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The Biot number is a dimensionless group that compares the relative transport
resistances, external and internal. It arises when formulating and non-dimensionalizing
the boundary conditions for the typical conservation of species/energy equation for
heat/mass transfer problems.
If your problem consists of an object suspended in a well mixed fluid, commonly you
only need to calculate the dynamics of the object (such as the temperature as a function of
position and time). If we focus on the fluid/object interface, the convective flux from the
bulk fluid to the object must equal the diffusive flux from the surface to the interior of the
object. This is typically formulated as a Robin boundary condition at the interface. For
. I N
example, consider the unsteady heat transfer in a solid sphere at initial temperature T0
submerged in a fluid of temperature T∞ (this is also the “bulk” temperature, and could be
given the symbol Tb).
V E
At the fluid-solid interface, the flux of heat into the sphere from the fluid must equal the
flux of heat from the surface of the sphere to the interior.
r r
qexterior = qinterior
S S
.B
r r
qexterior = h(Ts − T∞ )n
r
qinterior = −kT ∇T surface
W
The variables are defined as follows: q is the heat flux, h is the heat transfer coefficient in
r
W
the fluid, T is the temperature, n is the outwardly pointing normal from the solid, and kT
is the thermal conductivity of the solid. (Also recall that the heat transfer coefficient can
W
be obtained from correlations, and is basically just kT , fluid / δ T in systems without any
interfacial reactions or phase changes. The variable δT is the thickness of the thermal
boundary layer.)
dT
− kT
= h(Ts − T∞ )
dr
surface
*
I hope it is a review! TAs should be knowledgeable about this stuff if you have questions.
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T0 − T∞
This temperature variable starts out at 1 and decays to zero once the solid and fluid
A good dimensionless length is the inverse of the surface area to volume ratio:
SA 4πR 2 3r
η =r/L =r =r =
V (4 / 3)πR 3 R
L = R/3= O(R) in the case of a sphere so “L = R” would also be an okay choice. L is the
Using our definitions of dimensionless length and temperature, our Robin boundary
. I N
“typical” length scale that heat in the solid particle must diffuse to get to the surface.
condition becomes:
− kT
(T0 − T∞ ) dθ
= h(Ts − T∞ )
V E
L dη
surface
S S
.B
dθ hL
− = θ surface
= N Bi θ surface
dη surface
kT
N Bi =
hL
=
L / kT
=
W
"internal diffusion resistance"
kT 1/ h
W
"external convection resistance"
W
number on the problem.
Case 1: NBi<<1
dθ
− = N Bi θ surface
dη surface
Since θ surface
is at most one, in order for the equation to be true the surface gradient in
our dimensionless temperature is also small (as small as the Biot number). This means
that a good approximation to the dynamics can be found from a uniform temperature
throughout the sphere (a lumped system model). This means that the “external
convection resistance” dominates the problem, and the “internal diffusion resistance” is
†
“Big O Notation” is used to state in rough terms the magnitude of terms relative to each other, usually
only considering the order of magnitude or scaling
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small relative to the convection resistance so that it can be neglected when determining
the total resistance. (Think back to the “resistors in series” analogy in heat transfer.)
For example, a small heat transfer Biot numbers can arise in the case of a small
conductive metal sphere in a stagnant fluid such as air. The convection speed is very
slow (the resistance is large and h is small because the fluid is stagnant) and the
conduction speed is very high (the thermal resistance is small, or the thermal conductivity
is large, or the distance that heat has to diffuse in the object is very small).
Case 2: NBi>>1
On the other hand, if our Biot number is very large, the gradient must either be very large
at the surface or θ surface must be very small. However, since we scaled the derivative
dθ
properly, should be O(1). This means that θ surface
is very small. Recall that if θ
dη surface
is zero, this corresponds to the surface being in equilibrium with the bulk temperature (it
takes the bulk value). This simplifies our boundary condition for the problem so that we
can just use the condition that T (r = R) = Ts = T∞ and still get good results.
. I N
Mass Transfer Biot Numbers
E
In the case of mass transfer, the definition of the Biot number could get a little more
V
complicated because the partition coefficient between phases is involved. In this class,
S S
however, we aren’t worrying about partition coefficients, probably because we can’t
easily measure the internal concentrations anyway so we lump their effect into other
.B
unknown constants (such as the surface reaction rate constant).
The analogous case of a catalyst particle in a reactor fluid gives us the Robin boundary
condition:
r r
Wexterior = k m (c s − c∞ )er W
r dc r W
Winterior = −De
− De
dc
W dr surface
er
= k m (c s − c∞ )
dr surface
c − c∞
θ=
c0 − c∞
SA 4πR 2 3r
η =r/L =r =r =
V (4 / 3)πR 3 R
(c0 − c∞ ) dθ
− De = k m (c s − c∞ )
L dη surface
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dθ km L
− = θ surface
= N Bi,m θ surface
dη surface
De
In this case, we should take a practical look at the terms in the Biot number and see if it is
stuck in a particular range (always large, always small, etc.).
km L
N Bi,m =
De
D fluid
km = (stationary interface with no interface reaction)
δm
D fluid L
N Bi,m =
De δ m
The boundary layer is the largest it can be in a stagnant system, and in that case it is
approximately the same length scale as L. (Consider the example of the Sherwood or
Nusselt number for spheres in a stagnant medium.) Thus the ratio L / δ m is typically
greater than one.
. I N
V E
Also, the diffusivity of the species in the fluid is typically much greater than the effective
.B
Let’s consider the mass transfer Biot number definition again and consider what it means
in words:
N Bi ,m =
D fluid L
=
L / De
= W
"internal diffusion resistance"
>> 1
W
De δ m δ m / D fluid "external diffusion resistance"
So the consequence of this ratio is that whenever we are looking at a reactor where we
W
have bulk kinetic data, if we find out that we have an external diffusion limitation, we
However, we might not be all that concerned, because when you have an external
limitation, you may be able to predict the reaction rate purely by considering the surface
flux:
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Fo
FA
.B
(amount of “A” that exited) + (amount of “A” created inside the control volume) –
(amount of “A” destroyed inside the control volume)
dN A
= FAo − FA + GA
W
dt
GA [ = ]
moles
W
sec
W
If homogeneous, GA = rAV
else, GA = ∫ rA dV
where V is volume and rA is the rate of A created or destroyed (moles/sec/volume).
= v∇ρ A + D∇ ρ A + rA
2
dt
where v is velocity, D is the diffusion coefficient, and ρA is the molar density of A
(moles/volume).
Example:
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A+B→C+D
mole A
rA = − k [ A][ B ] , rC = + k [ A][ B ] , [ A][ = ]
liter
where k is a measurable rate constant that changes with respect to T and P but
remains constant with respect to changing concentrations.
If r1 = k [ A][ B ] , then
P
=−1
rA = ν A,1 r1
where ν A,1 is the stoichiometric coefficient for species A in reaction 1. Likewise,
P=+1
rC = ν C ,1 r1
GA (t ) = ∫∫∫ rA ( x, y, z, t )
dxdydz
. I N
P NA V
d [ A]
[ ][
Vol . - k (T ( x , y , z ,t )) A( x , y , z ,t ) B ( x , y , z ,t )
]
V E
dt
= − k [ A][ B ] → *only true if there are no flows!
S S
.B
dN A
= ∫ rA dV ≈ rAV , assume rA is true throughout volume
dt
Extent of Reaction
ξ [ =] moles, extent of rxn.
moles
ξ [ = ] , rate of extent of rxn.
sec
A+ B → C + D
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Conversion
A+ B → C + D
N − NA
X A = A,initial (dimensionless)
N A,initial
NC
XC = ( ≈ 1 since rxn is 1:1)
N A,initial
⎛ A+ B → C + D⎞
⎜
⎝ A →U
⎟ Selectivity is good if A → C , bad if A → U .
⎠
*May worsen as rxn. goes on ( A → C slows, A → U keeps going)
. I N
V E
S S
.B
W
W
W
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The lecture covers: Definitions in terms of reacting compounds and reaction extent,
rate laws, Arrhenius equation, elementary, reversible, non-elementary, catalytic
reactions.
Example:
A + B → 2C
*Reactions are reversible (often will neglect reverse)
N Ao − N A FAo − FA FC
XA = XA = XC =
N Ao FAo 2 FAo
A,B
FAo
C,A,B
. I N
FBo
V E
Figure 1. A reactor with reactants A and B constantly flowing in and product C and
unused reactants A and B flowing out.
FAo =
moles A flowing in
= [ A]input vin = [ A]o vo
S S
sec liters
sec
.B
FA =
moles A flowing out
sec
= [ A]output vout
W
X = 1−
[ A]output vout
[ A]in vin
W
W
Closed reactor, const. V
d [ A]
= rA = − k [ A][ B ]
dt
[C ]
2
K eq =
[ A][ B ]
[C ]
2
⎛ [ C] ⎞
2
k
rA = − k [ A][ B ] −
⎜ ⎟ , krev = for , forward-reverse in one expression
⎜ K eq ⎟ K eq
⎝ ⎠
same!
Catalysis
Rate limiting step determines the kinetics (slow step). The kinetics are insensitive to
[B] because B is not part of this slow step.
[C ]
2
V E
A→ B+C
[ B ][C ] = moles
[ ] S S
.B
K eq =
[ A] liter
KC
Partial Pressures
[ B ][C ] W
pB pC
pA Po
= K eq =
W Po
[ A] RT
Ideal Gas: pV = nRT ⇒
W n
=
V RT
P
Po is the standard state pressure (1 atm), this makes the units cancel. Using partial
pressures is accurate within 10%, more error with liquids.
Stoichiometric coefficient
N A = N A,initial + ∑ν A,iξi
Extent of rxn.
N rxn
N C = N C ,initial + ∑ν C ,iξi
i =1
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column column
vector vector matrix vector
N = No + ν i ξ
NC Reaction trajectory-
Plot state of system
ξ=ΝΑο
t=10
ξ
d
(N ) = F (N)
t=0.01
NB
dt
. I N
ξ1=0
V E
NA
S S
.B
Figure 2. A plot of the reaction trajectory. ξ is the extent of reaction.
Conservation Laws
W
Conserve atoms
2CH 4 + O 2 → C2 H 4 + 2H 2 O W
constant moles
W
C A N A + CB N B + CC N C = const.
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This lecture covers: cell growth kinetics, substrate uptake and product formation in
microbial growth, enzyme kinetics, and the Michaelis-Menten rate form.
For a hypothesized mechanism, we can often derive an exact, closed form analytical
solution.
If not, it’s used to approximate:
-some reactions go rapidly to equilibrium
. I N
-the concentrations of some species rapidly reach their steady state values
-the rate-limiting step
Or, as a last resort- numerical solution
V E
S S
X=first order − rA = kC A
.B
-rA =second order −rA = kC A 2
X
=zero order −rA = k
X
X
W
X
X
W
W CA
Figure 1. Rate versus concentration graphs for zero, first, and second order
reactions.
Enzymes-Biological Catalysts
S=Substrate
E=Enzyme
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Activation energy
decreases with E
(enzyme)
Energy
P
Reaction Progress
Figure 2. An energy diagram for a reaction with and without an enzyme. The
activation energy is lower with an enzyme, so the reaction proceeds faster.
CS Initial Rate
dCS
− rS = −
dt t =0
Time
. I N
initial rate.
V E
Figure 3. The slope of the concentration versus time curve at time = 0 can give the
Michaelis Menten S S
~1st order
.B
-rS
W
~0th order
X
X
W
X X X X
X
X
X
W
X
What gives change
from 1st order to 0th
order?
X
CS
Hypothesized Mechanism:
-Encounter complex ES formed
-Irreversible reaction occurs In more complex cases,
-Rapid release of product from complex these are not always true
-Assume rapid equilibrium is reached in the formation of ES
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Later, Briggs-Haldane derived a law with steady state assumption for ES and they
got the same rate law as Michaelis-Menten. However, the Briggs-Haldane method is
more generally applicable.
ZZZ
E + S YZZ1
X k
Z ES
k −1
ES ⎯⎯→ E + P
kcat
dCES
Steady state assumption on ES → =0
dt
CE ,0 = CE + CES
because CE ,0 CS ,0
. I N
0 = k1 (CE ,0 − CES )CS − CES (k−1 + kcat )
V E
Cs ≈ CS ,0
S S
.B
Solve for CES (steady state solution)
CE ,0CS
CES =
k−1 + kcat
k1
+ CS
W
− rS = rp =
dC p
W
= kcat CES =
kcat CE ,0CS
k−1 + kcat
V C
= max S
+ C S K m + CS
W
dt
k−1 + kcat
Km = = Michaelis constant
k1
This model fits the data:
Vmax
-As CS K m , − rS → CS
Km
-As CS K m , − rS → Vmax
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-rS
X X X
X The rate flattens out
X
because all of the
X
X enzyme is bound.
X
X
X
CS
. N
-Steady state is defined over a limited period of time. Because there is an
I
-Equilibrium assumption is not exactly correct. The irreversible step prevents
true equilibrium.
V E
Growth Kinetics
S
A population of single cells, growing without limitations S
.B
N=#cells per volume
dN
= μ N , μ = constant, specific growth rate
dt
W
N = N 0e μ t − exponential growth while true, "Malthusian growth"
Growth Stops W
W
-Run out of nutrients
-Accumulate toxic byproducts
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dN μ C
= max S N
dt K S + CS
We will return to this when we
dCS −1 look at bioreactors
= μN
dt Yx s
I=inhibitor or toxin
μ μ ∝ e − kC I
1
μ∝ All forms fit the data
(1 − kCI )
kI
μ∝
k I + CI
CI
I N
Figure 6. Growth rate versus concentration of inhibitor. Many functional forms fit
the curve.
.
V E
S S
μ .B CS=concentration of growth limiting
X
X X X
W substrate, often glucose
X
X
X
W
X
X
X
W KS
CS
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CH1.8O0.5N0.2
(for a typical microbial culture)
g biomass
For glucose, Yx s ≈ 0.6 ± 0.1
g glucose
g biomass
For oxygen, Yx O2 ≈ 1.9 ± 0.7
g O2
. I N
V E
S S
.B
W
W
W
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A+B
Stable molecules: neutral, closed shells
()
(e)
(+)
nucleus
nucleus
bond
Figure 1. Stable molecules.
. I N
Pauli Exclusion Principle
You can’t put 2 identical e in the same exact spot
V E
S S
.B
Figure 2. Two electrons in an orbital have opposite spin.
Bond Forming
W
0 e 2 e
W
+
empty
orbital
W +
H H
H H
Figure 3. Bond formation. On the left, an empty orbital receives two electrons from
another orbital. On the right, halffilled orbitals on the H atom mix to form a filled
bonding orbital with two electrons.
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Boltzmann Distribution
R
p ( E ) ∼ e − E k BT kB =
NA
E ≫ k BT → very unlikely
E A + EB > E Activation
Barrier
A B
collide correctly
and react
k (T ) ∼ Ae − Ea k BT
A is the prefactor, proportional to the number of ways the molecules get together
with sufficient energy to react.
Reactive Intermediates
charged
empty orbital
acid/base chemistry
single e orbital
metal catalyst
free radical
. I N
Example:
V E
RC
O
OR + H2O ⇌ RC
O
OH + ROH
S S
(endo
O
.B
k1
OH + RC OR ↽
O
⇀ k2
thermic)
RC OR → R
W O
OH
+ RO
k3
→
O
O
+ ROH
W
k−1 R
OH (acid) minor
(base catalyzed) species
W O
minor
species
(SS)
(SS)
O
+ H2O ⇌ + OH
R
O R OH
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O O
k1 OH
d RC OR
O
RC OR ≈ RC OR
OH k−1 + k2
≈0 OH
dt
O
k2 RC OR
d [RO ]
≈0 RO ≈ OH
dt k3 [acid]
O kk O
rROH = k3 RO [ acid] = k2 RC OR = 1 2 OH
k−1 + k2 RC OR
OH
keff
Rate Limiting Step
N
Only 1 rate constant of keff is really relevant
What do you have most of in a reaction mix? This is the material preceding the rate
limiting step.
O
E . I
V
O
RC OR + H2O ⇌ RC OH + ROH
OH
S S
.B
O O
RC OR →
k2
k1
+ ⇀
H + RC OR ↽ + R+
k−1
+ R OH
W
(acid) minor
(acid catalyzed)
species
(SS)
(SS)
R
+
+ H2O
→ ROH+H
k3
W +
d RC
+
OH
W
OR
≈0
OH
RC OR ≈
+
k1
H
+
O
RC OR
k−1 + k2
dt
OH
k2 RC OR
d [R + ] +
≈0 R + ≈
dt k3 [H2O
]
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OH kk O
rROH = k3 R+ [H2O] = k2 RC OR = 1 2 H+
+ k −1 + k 2 RC OR
keff
Ethylene
(in plastics)
C2H6 → H2 +C2H4
Ethyl radical
C2H6 + H → H2 + C2H5
i i
C2H5 → C2H4 + H
i i
C2H6
slow
→ 2CH3i inefficient, but important (radical creation)
CH3
i
+ C2H6 → CH4 + C2H5i
→ C2H6 + C2H4
N
i
2C2H5 (radical destruction)
(disproportionation)
E . I
S V
.B S
W
W
W
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This lecture covers: Reactions in a perfectly stirred tank. Steady State CSTR.
Batch Continuous
Open system
Steady State
Open system Well mixed
Close system
Steady State
Well mixed
Continuous
Transient
. I
Figure 2. A batch reactor. Figure 1. A plug flow reactor, and continuous stirred
tank reactor.
N
Mole Balance on Component A
In-Out+Production=Accumulation
V E
FAo − FA + rAV = 0 (steady state)
S S
.B
FAo − FA
V= FA = FAo − X A FAo
−rA
W
In terms of
conversion, XA?
W
V=
FAo X A
−rA
W
What volume do you need for a certain amount of conversion?
where rA is evaluated at the reactor concentration. This is the same as the exit
concentration because the system is well mixed.
C Ao X A
τ=
−rA
. I N
We can now define a “Damköhler number”
Da =
reaction rate − rAoV
=
V E
, rAo is the reaction rate law at the feed conditions
flow FAo
S
st
For a liquid at constant pressure with 1 order kinetics: S
Da = kτ
Da .B
⇒ XA =
1 + Da
W
therefore:
As DaÆ, XAÆ1
W
As Da∞, XAÆ0 (molecule probably leaves before it can react)
W
For a liquid at constant pressure with 2nd order kinetics:
− rA = kC A2
= kC Ao 2 (1 − X A )
2
C Ao X A C Ao X A XA
τ= = =
−rA kC Ao 2 (1 − X A ) kC Ao (1 − X A )
2 2
XA =
(1 + 2τ kC Ao ) − 1 + 4τ kC Ao
2τ kC Ao
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kC Ao 2 V
Da = = τ kC Ao
C Ao vo
Thus, conversion can be put in terms of Da.
XA =
(1 + 2 Da ) − 1 + 4 Da
2 Da
How long does it take for a CSTR to reach steady state?
In-Out+Production=Accumulation
dN A
FAo − FA + rAV =
dt
For a liquid at constant density this is:
dC A
C Ao − C A + rAτ = τ
dt
Ænon-dimensionalize
C t
Cˆ A = A tˆ =
C Ao τ
τ C Ao dCˆ A
C Ao − C Ao Cˆ A − kC Ao Cˆ Aτ =
dCˆ A ⎛ P ⎞ ˆ
Da
τ dtˆ
. I N
+ ⎜ 1 + kτ ⎟ C A = 1
dtˆ ⎜⎝ ⎟
⎠
V E
dCˆ A
dtˆ
+ (1 + Da ) Cˆ A = 1
with initial conditions:
S S
Cˆ A = 0, tˆ = 0
we have the solution: .B
Cˆ A =
1
(
1 − e− (1+ Da )t
ˆ
) W
1 + Da
W
In nondimensional terms, it exponentially approaches a new steady state with a
τ
W
characteristic time
1 + Da
.
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Cˆ A
1
1 + Da
1
tˆ
1 + Da
Figure 3. Approach to steady state in a continuous stirred tank reactor (CSTR).
The time at which ½ of the steady state concentration of CA is achieved is the half
ln(2)
time: τ
1 + Da
CSTRs in Series
. I N
(Liquid and at constant pressure)
CA0
V E
S S
.B
Da1
W
Da2
CA2
W
Figure 4. Two tanks in series. The output of the first tank is the input of the second
tank.
C A1 =
C A0
1 + Da1
W
1st order reaction kinetics
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This lecture covers: Selectivity vs. conversion and combining reactors with
separations.
A Optimal
Purer P
P, A, U Separator
(A, U)
product byproducts
Figure 1. Schematic of a reacting system with a recycle stream.
const. (vol.)
. I N
Simple Target: maximize Fp = rp ⋅V
V E
S
rp (concentrations, T) S
Constraint: T ≤ Tmax
High temperature Æ maximum rate constant .B
Simplest Case:
W
A→ P
W
rp = k [ A] [ A] ⇒ [ A] feed
τ →0
W
Fp = [ P ]V0 = [ P ]
V
residence
time in reaction
τ
(1− e − Da )
= Vk [ A] feed
Da
Constraint: [ P ] ≥ [ P ]min (purity constraint )
Æ X ≥ X min conversion
{ }
Fp = k (Tmax ) [ A]0 − [ P ]min V = k (Tmax ) [ A] feed V (1− X )
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A + B → 2C 2nd order
rc = 2k [ A][ B ]
A, B
[ A] = [ A] feed (1 − X A )
[ B ] = [ B ] feed (1 − X B )
.1 .1
[ A][ B ][C ] rc = 2k [ A] feed [ B ] feed (1 − X A )(1 − X B )
.01
Figure 2. Schematic
of a CSTR.
A, B
B
[ B ] [ A]
Separator
recycle stream.
. I
Figure 3. A reacting system with
N
A, B, C
V E
product may
(A)C
S S
A→ B
B→C
also react
.B
A →U
undesirable
W
W
FB = f ([ A] , [ B ] , [C ] , [U ] ,τ , T )
6 variables
W
Æ fsolve (Matlab)
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Simplest Case:
k1 (T )
A→B
k2 (T )
B→C
k3 (T )
A→U FA
[ ]
A = in
V (k1 + k3 + 1 )
τ
[U ] = k3 [ A]τ
[C ] = k2τ [ B ]
k [ A]
[ B] = 1 1
k2 +
τ
FAo k1τ
N
FB (τ , T ) =
(k1τ + k3τ + 1)(1+ k2τ )
N N N
. I N
optimize
2 variables
Da1
Æ contour plot
Da2 Da3
V E
S S
.B
Figure 4. Sample contour plot for the 2-
W
variable optimization.
matlabÆfmincon
(allows for constraints) W
∂FB
∂T
= 0,
∂FB
∂τ
=0
W
Don’t use these – you may not find an actual optima.
FP
Yield ≡
FA0
Yield A→ P ≡ X A S A→ P
FP
Selectivity =
S A→ P ( FA0 − FA )
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Y
P
A → P →U
→
A
P →U
τ
Figure 5. Yield versus residence time. Intermediate P rises in
concentration and then falls off as it is converted to U.
. I N
V E
S S
.B
W
W
W
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A → B
r = k[ A]
q [A]0
V [A] [B]
The goal is to maximize FB with respect to changes in the volumetric flow rate, q.
FB = q[B]
W
Continuing with the material balances, we find:
[ A] =
[ A]0
W =
[ A]0
1+ (kV / q ) 1+ kτ
W
When Da = kτ << 1, [A] goes to [A]0.
FB = rV = kV[ A] = =
1+ kτ 1+ kV / q
⎛ kV[ A]o ⎞
lim FB = lim⎜⎜ ⎟ = kV[ A]0
⎟
⎝ 1+ kV / q ⎠
q→∞ q→∞
Unfortunately, in the limiting case of infinite flow rate, the concentration of B in the
output solution is vanishingly small:
⎛ [ A]0 ⎞
lim[B] = lim(k[ A](V / q )) = lim⎜⎜ k (V / q )⎟⎟ = 0 .
⎝ 1 + (kV / q ) ⎠
q→∞ q→∞ q→∞
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materials for 10.37 Chemical and Biological Reaction Engineering,
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30
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This lecture covers batch reactor equations, reactor sizing for constant volume and
variable volume processes.
Batch Reactors
Batch CSTR
CSTR.
. I N
Figure 1. Schematics of a batch reactor and a
Flexibility
Expensive Reactants
S
+
+ S -
Material Balance
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dN A
rA V =
dt
dC A
Constant V, rA =
dt
dX A
In terms of conversion, C Ao = rA
dt
CA dC A X A dX
Integrating, t=∫ or t = C Ao ∫ A
C Ao r 0 r
A A
− rA = kC A = kC Ao (1− x A )
xA dx A 1 ⎛ 1 ⎞
t = C Ao ∫ ⎯⎯
→ t= ln ⎜ ⎟
0 − kC Ao (1 − x A ) k ⎝ 1− x A ⎠
xA = 1 − e −kt
V E
k
S S
2nd Order Reaction A + A ⎯k⎯
→B
.B
−rA = kC A2 = kC Ao 2 (1− X A )2
W
t = C Ao ∫
0
XA dX A
−kC Ao (1 − X A )
2 2
W
=
1
−kC Ao ∫0
XA dX A
(1− X A ) 2
t=
1 XA
kC Ao 1− X A
W XA =
kC Aot
1+ kC Aot
1 2 3
1st order 0.63 0.86 0.95
2nd order 0.50 0.67 0.75 }x A
For a given Damkohler number, 1st order is faster. The second order reaction has
greater concentration dependence. Exponential approach (1st order) is faster.
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Batch Cycle
t
Time
Charge rxn Discharge Clean
Downtime, td
Pr(Rate of Production) =
(toptimum + td )
dX A
− XA = 0
dt
.B (toptimum + td ) 2
dt
W
W
Now specify kinetics. There may be no optimum.
1st order
W X A = 1 − e− kt
dX A
dt
= ke− kt
− ktoptimum − kt
(toptimum + td )ke − (1− e optimum ) = 0
Can numerically solve for toptimum .
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Semi-batch Reactor
or
slow
feed of
. I N
A
V
Figure 3. A fed-batch E
B one reactant.
S S
reactor with a slow feed of
•
.B
To shift equilibrium, strip off product
•
•
W
To control evolution of heat
In biological cases
Fed-batch
W
- Feed in carbon source slowly to avoid overflow metabolism
- (glucose)
- O2 sparingly soluble, must feed.
2) Balances
A Balance
W B
Figure 4. Fed-batch
reactor with a feed of B.
A
d (rA V)
rA V(t ) =
dt
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dC A dV
rA V(t ) = V + CA
dt dt
Liquid V = V0 + v0t
flow
dilution
dC A v
= rA − 0 C A
dt V0
B Balance
dCB v v
= rB + 0 CBo − 0 CB
dt V0 V0
N
Addition Dilution
. I N
V E
S S
.B
W
W
W
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rA = −k [ A]
2
X A FAo = −rAV
X A FAo
VCSTR = nd
(2 order reaction)
k [ A]0 (1− X A )
2 2
XA
treact . =
k [ A]0 (1− X A )
VBatch ( [ A] ) = ?
0
N
FAo XA
VBatch = ⎢t d + ⎥
Assume XA=90%
[ A]0
If treact>td then
⎣⎢ k [ A]0 (1 − X A ) ⎦⎥
E . I
VBatch =
2FAo ⋅ 0.9
[ A]0 k [ A]0 (1− 0.9 )
S V
VCSTR =
0.9FAo
k [ A]0
2
≤
1.8FAo
k [ A]0
2
.B S
W
W
W
Figure 1. Three tanks in series.
V
[ A]CSTR = [ A]in + rA
v0
If rA = − k A [ ]
[ A]in [ A]in
[ A]out = =
kV
1+ Da 1+
v0
If n CSTRs are in series:
V
each volume =
n
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[ A]in
[ A]out = n
⎛ kV ⎞
1+ ⎜ ⎟
⎝ nv0 ⎠
Æimproves productivity:
concentration of A in 1st one is higher than would be in one large CSTR
− kV
[ A]out
Batch
= [ A]0 e v0
kV
= 3 ⇒ 95% conversions
v0
[ A]0 N XA
[ A]CSTR
out = n 1 .75
series ⎛ 3⎞ 10 .93
⎜1+ ⎟
⎝ n⎠ 100 .948
. I N
PFR
Figure 2. Diagram of a plug flow reactor.
V E
FAin − FAout + rA ( ΔV ) = 0 CSTR
S S
Plug Flow Reactor (behaves like an infinite number of infinitely small CSTRs)
⎛ FAin − FAout ⎞
⎜
⎝ ΔV ⎟ = −rA
⎠ .B
dFA
= −rA design equation for PFRW
dV
dFA
= r ( C A ,CB ,...) W
dV
W
= −kC ACB (for example)
FA = C Av0
dFA F F
= −k A B
dV v0 v0
dY
This can be expressed as: = F ( t ,Y ) where t is replaced by V.
dt
Example:
ZZZ
A + B YZ ZX
ZC
k
k rev
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⎛ kFA FB krev FC ⎞
⎜− + ⎟
⎜ v02 v0 ⎟
⎛ FA ⎞
d ⎜ ⎟ ⎜ kFA FB krev FC ⎟
FB = ⎜ − + ⎟
dV ⎜⎜ ⎟⎟ ⎜ v02 v0 ⎟
⎝N FC ⎠
⎜ kF F k F ⎟
Y ⎜⎜ + A2 B − rev C ⎟⎟
⎝v0
v0 ⎠
F ( t ,Y )
z
Figure 3. Diagram of a plug flow reactor showing flow in the z-direction.
dV = area ⋅ dz
V E
d ( vρ A)
dz
dv
= ρ A + ρv
dz
dA
dz
+ Av
dρ
dz
=0
S S
Rearrange:
dv ⎛ 1 dA 1 d ρ ⎞
= −v ⎜ + ⎟ .B
dz ⎝ A dz ρ dz ⎠
dA W dρ
For a normal pipe
dz
W
= 0 and for a liquid
dz
=0
Therefore:
dv
dz W
= 0 ⇒ v = v0
(We can’t assume this for gases!)
For a PFR:
dFA
= rA
dV
FA = v [ A]
d ( vC A )
= rA
dV
For liquids, v is constant so we can take it out of the differential.
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v dC A
rA = , for liquids
area dz
dC A area
= rA
dz v0
Instead of treact we have zreact!
area ⋅length
t pipe =
v0
area ⋅ z XA
t PFR = =
v0 k [ A]0 (1− X A )
P0 Pfinal
Figure 4. Diagram of a pipe showing pressure upstream and downstream.
PV = NRT
P
∑ Ci = RT
. I N
Ci =
P Fi ⎪
⎫
⎬ turns F's into concentrations
V E
RT ∑n Fn ⎪⎭
ρ = ∑ CiWi , Wi is molecular weight of i. S S
v=
mass flowrate
← const.
.B
ρ (z)
W
W
W
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This lecture covers reactors in series and in parallel, and how the choice of reactor
affects selectivity versus conversion.
Material balance:
CSTR PFR
FAo XA FAo
V= XA V=∫ dX A
−rA 0 −rA
“Levenspiel Plot”
• as X A increases, C A decreases
FAo F
. N
−rA decreases, for 1st and 2nd order,
I
− rA 1st or 2nd
order
so Ao increases
−rA
V E
reaction
S S
Figure 1. General Levenspiel Plot.
XA .B
CSTR Volume W PFR Volume
W
FAo
W FAo
− rA − rA
VCSTR VPFR
XA XA
Figure 2. Levenspiel plots for a CSTR and a PFR for positive order reactions.
So PFR is always a smaller reactor for a given conversion when kinetics are positive
order.
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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Series of Reactors
Example: 2 CSTRs
FAo
v1
x1
FA1
. I N
v2
V E
FA2
S
x2
S
.B
Figure 3. Schematic of two CSTRs in series.
F
V1 = Ao X 1
−rA1
W
2nd reactor:
In + Out + Prod = Acc
0
W
W
FA1 − FA2 + rA2 V2 = Steady state
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FA0
FA2 = FA0 − X 2 FA0 → V2 = ( X 2 − X1 )
−rA2
FAo
− rA
V1 Figure 4. Reactor volumes for 2 CSTRs
V2 in series.
X1 X2
X
I N
Multiple CSTRs begin to
.
approximate a single PFR
FAo
− rA
V E
S S
.B
X
W
W
Figure 5. Reactor volumes for multiple CSTRs in series.
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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FAo FAo
− rA − rA VCSTR
VPFR
VPFR
VCSTR
X XA
Final X
Designed final
conversion
Figure 6. Levenspiel plots comparing CSTR and PFR volumes for changing kinetics.
Left: The CSTR has the smaller volume. Right: The PFR eventually has the smaller
volume.
Choice of PFR vs CSTR depends on conversion. Choose the reactor that has the
smallest volume Æreduce cost.
. I N
Reactors:
V E
FAo
S S CSTR
−rA
VCSTR
.B
W VPFR
W PFR
W X
Final X
Figure 7. To achieve the desired conversion with smaller reactor volumes, use a
combination. In this case, use a CSTR then a PFR. By doing so, the reactor volume is
less than the area underneath the curve.
For competing parallel reactions, selectivity for desired product can dominate the
choice.
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rD kd (α1 −α 2 )
Define “selectivity” SD /U = = CA
rU ku
dCD kd C αA1
φ= =
− dC A kd C αA1 + ku C αA 2
V E
ΔC A = C A − C A
0
A
S S
For a PFR: Φ=
1
ΔC A ∫
C At
CA 0
φ dC A
.B
If α1 = α 2 W
W
φ
W ΦΔC A
C Af C A0
CA
Figure 8. Fractional yield versus concentration. Selectivity does not depend on CA.
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If α1 > α 2
CA
Figure 9. Fractional yield versus concentration when α1 > α2.
CSTR PFR
φ φ
Φ PFR ΔC A
Φ CSTR ΔC A
. I N
C Af
CA
C A0
V E
C Af
CA
C A0
S S
Figure 10. Comparison of overall fractional yield for a CSTR and a PFR when α1 >
α2.
.B
PFR is preferred because Φ PFR >Φ CSTR , therefore the yield of D per mol A consumed
is higher.
W
If α1 < α 2
W
φ
W Φ CSTR ΔC A φ Φ PFR ΔC A
C Af C A0 CA C Af C A0 C A
CSTR PFR
Figure 11. Comparsion of overall fractional yield for a CSTR and a PFR when α1 >
α2.
Φ PFR <Φ CSTR
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 9
Prof. K. Dane Wittrup Page 6 of 6
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This lecture covers residence time distribution (RTD), the tanks in series model, and
combinations of ideal reactors.
NonIdeal Mixing
CSTR PFR
Figure 2. Ideal CSTR with pulse input. A pulse input will yield an output profile that
is a sharp peak with a tail.
. I N
bypassing
V E
mixing
S S
.B
recirculation
eddies
W
stagnant
volumes
W
W
Figure 3. A real mixed tank. In a real mixed tank there are portions that are not
well mixed due to stagnant volumes, recirculation eddies, and mixing bypasses.
In a real PFR there is backmixing and axial dispersion. In a packed bed reactor
(PBR) channeling can occur. This is where the fluid channels through the solid
medium.
E ( t ) dt ≡ Probability that a fluid element entering the vessel at t=0 exits between
time t and t+dt.
∫ E ( t ) dt
0
Probability that fluid element exits before time t.
∫ E ( t ) dt
t
Probability of exiting at time later than t.
∞
mean t = tE ( t ) dt = τ
∫
0
∞
normalized = ∫ E ( t ) dt = 1
0
∞
∫ ( t − τ ) E ( t ) dt
2
variance = σ =
2
(measures the broadness of the distribution)
0
E
before t1
after t1
. I N
V E
t1 t
S S
.B
Figure 4. E(t) versus t. At a given time point, some material has exited and some
material will still exit at a later time.
pH
saltconductivity
radioactivity
W
Use one of two types of input concentration curves:
Pulse Step
Cin Cin
t t
Figure 5. Two types of input. A pulse input is a spike of infinite height but zero
width, ideally. A step input is a constant concentration over a period of time.
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 10
Prof. K. Dane Wittrup Page 2 of 7
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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A pulse input allows for easy interpretation because all materials enter the reactor at
once.
Cin Cin
t detector t
input
curve
Cout ( t )
E (t ) = t
∫ C ( t ) dt
0
out
PFR (Ideal)
. I N
V E
Cin Cin
S S
t0 t
.B τ
t
W
Figure 7. Pulse input in ideal PFR. A pulse input in an ideal PFR becomes a pulse
output.
E (t ) = δ (t −τ )
W
= 0
δ ( x) =
∞
= ∞
W x≠0
x=0
∫ δ ( x ) dx = 1
−∞
∞
∫ f ( x ) δ ( x − a ) dx = f ( a )
−∞
CSTR (Ideal)
Transient material balance:
InOut+Production=Accumulation
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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Since all the material is added at once, In=0. The tracer used is nonreactive.
Therefore there is no production. This gives:
dC
0 −ν 0 C + 0 = V
dt
−t V
C ( t ) = C0 e τ
, τ=
ν0
−t
C (t ) e τ
E ( t ) =
∞ =
τ
∫ C ( t ) dt
0
CSTR
Figure 8. Pulse input in an ideal CSTR. In an ideal CSTR, a pulse input leads to a
sharp peak with a tail.
. I N
mean residence time =
∞
∫
te
τ
−t
τ
dt = τ
V E
0
S S
CSTR (nonideal mixing)
Bypassing: Divide input into 2 streams
.B
ν0
νB W
W
V
W
ν SB
ν0
Figure 9. A bypass is modeled by dividing the input stream into two streams, one of
which does not enter the reactor.
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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t t
combine
E
V
Perfect mixing τ=
ν0
Bypass τ = V
t ν SB
Figure 10. Residencetime distribution determination for a bypass.
E
. I N
VSD
ideal
V E
VD
dead volume
present
S
t
S
.B
Figure 11. Residencetime distribution for dead volumes. When a dead volume is
present, a decreased amount of material is observed in the output stream.
measureable V=VSD+ VD
W
τ SD =
VSD
ν0
< τ ideal
W
PFR (Nonideal)
Channeling
W
channeling
bed
channel
PFRlike
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Axial Dispersion
Figure 13. A pulse input can become an axially dispersed pulse output in a nonideal
PFR.
Tanks in a series
To model the PFR as several tanks in a series, break the reactor volume, V, into n
V
CSTRs of volume each.
n
1 2 3 n
. I N
is sampled at tank n for dispersion.
t n −1
V E
Figure 14. n tanks in series. The output of tank 1 is the input to tank 2. The output
τ
S
−t
E (t ) = e τi , τ i =
( n − 1)!τ i
S
n
n
E(t) 10
PFR
.B
1
W
W
2
W 4
Figure 15. E(t) plots for 1, 2, 4, and 10 tanks and a PFR. Notice how the E(t) curve
approaches the PFR pulse as more tanks are used.
The numbers above represent numbers of CSTRs. Without enough CSTRs, the peak
is not a good approximation to the narrow peak for a PFR when there is a pulse
input.
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τ2
σ2 =
n
τ 2
n=
σ2
We can physically measure τ and we can determine σ from experimentally measuring
E(t).
RTD (residence time distribution) are useful for diagnosis, but not for reactor design.
. I N
Figure 17. Partially dead volumes. Dead
volumes can be modeled as separate
V E
S
CSTRs that exchange material with each
other.
.B S
W
W
W
Figure 18. Bypass. A
bypass can be modeled
as a CSTR along one
route with a PFR along
the bypass route.
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This lecture covers: Derivation of energy balances for ideal reactors; equilibrium
conversion, adiabatic and non-adiabatic reactor operation.
Non-isothermal Reactors
dN i N streams N rxns
= ∑ Fi ,m + Vcv ∑ υi ,l rl
dt m =1 l =1
stoichiomet
stoichiometric
ric
coefficient
rl - depends on concentration
-T
- catalyst
dU cvtotal
dx
dV N streams
flow work
extensive
work
intensive heat
shaft V
do work Æ
S Ws negative
expansion
work
.B S
work
W
If small control volume, pressure constant.
P1
W P2 P1 ≠ P2
W
In Vcv1 has a
fixed P
other control
volumes
Figure 1. Schematic of a PFR with small control volumes, each with a fixed P.
PFR has many small control volumes, each with its own constant P.
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Where is T? In U cv and rl (T ) .
total
dN i
heat capacity intensive substitute for
of system contribution of dt
each species
dY
Want = F (Y )
dt
Assume ideal mixtures
U cvtotal ≈ ∑ N iU i (Tcv )
extensive intensive
. I N
dU
dN i
total
= U i (Tcv )
cv
V E
If P=Constant (Isobaric)
S S
.B
dH total d (U + PV ) dU dP dV
= = + V +P
dt dt dt Ndt dt
W
0
total
dU dV
+ P cv
cv
dt
dt
↓
W
dH
dt
total
W
Assume isobaric, all ideal mixtures, neglecting K.E., P.E., other energies
− ∑ ∑ H (T
i l
i cv )Vcvυi ,l rl (Tcv ) + Q +Ws
∑υ
i
i ,l H i (Tcv ) ≡ Δ H rxn (Tcv )
l
stoichiometric coefficient
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N streams N rxns
− ∑ ∑ H (T
i l
i cv )Vcvυi ,l rl (Tcv ) = −∑ Vcv rl (Tcv )Δ H rxn (Tcv )
l l
Assume
coolant
heat reactor
transfer
coefficient
area of
contact
. I N
Chapter 8 in Fogler – lots of special case equations
– be careful of assumptions
V E
Special case: Start up CSTR to a steady state
want to know ultimate T
S S
dTcv N streams N species
.B
= 0 ≅ ∑ ∑ Fi ,m ( H i (Tm ) − H i (Tcv ) ) − ∑ Vcv rl Δ H rxn +UA(Ta − Tcv )
dt m i
W l
W
When we reach steady state, no more accumulation
If just one reaction, one input stream, one output stream, and the system is at
steady-state:
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⎛ ⎞
⎛ Fi , in ⎞ ⎜ UA ⎟
R(T ) = ⎜ ∑ C p, i ⎟ ⎜1 + ⎟ (T − Tc )
⎝ FAo ⎠ ⎜
⎜
∑ Fi, inC p , i ⎟
⎟
⎝ K ⎠
Heat removal
K =0 Adiabatic
K = Big Cooling
Tc =
KTa + Tin
. I N
1+ K
.B
cool W R(T )
Three steady-state solutions
W
a lot • −ΔH rxn
G (T )
W •
•
T
Figure 2. Graph of G(T) versus T. Three steady-state points are shown where R(T)
intersects with the heat of reaction.
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Continuing the stability and multiple steady-state discussion from Lecture 11:
R (t ) removal of heat
generation
•
Treactor
Figure 1. Three steady-state conditions shown on a G(T) versus T graph.
. I N
⎛ ξ1 ⎞
V E
⎜ ⎟
⎜ ξ 2 ⎟ = z SS
⎜T ⎟
⎝ ⎠ SS
S S
dξ1 .B
dt
dξ 2
=0
W
steady-state
dt
=0
W
dT
dt
=0
W
⎧ dξ1 ⎫
⎪ dt = f1 (ξ1 , ξ 2 , T ) ⎪
⎪ ⎪ vector notation
⎪ dξ 2 ⎪ dz
original eqns. ⎨ = f 2 (ξ1 , ξ 2 ,T ) ⎬ → = F ( z)
⎪ dt ⎪ dt
⎪ dT ⎪
⎪ dt = f 3 (ξ1 , ξ 2 , T ) ⎪
⎩ ⎭
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d
i.e. (δ z ) = (−ve)δ z
dt
δz what does perturbation cause?
• - back to steady-state or off elsewhere?
Figure 2. A small perturbation moves the system away from steady state. Does the
system move back or does it move to elsewhere?
dz
= F( z)
dt
#
z = z SS + δ z δ z = z − z SS
d dz
(δ z ) = = F (δ z + z SS )
dt dt
≈
dF
dz
0
δ z + F ( z SS ) + O(δ z )
2
0
. I N
Jacobian matrix
⎛ dF ⎞
V E
d
dt
(δ z ) = ∑ ⎜ n ⎟ δ zm
⎝ dzm ⎠ z SS
S S
= Jδz
.B
⎛ df1
⎜
⎜ dξ1
df1
dξ 2
df1 ⎞
dT ⎟ W
⎟
⎜ df
J =⎜ 2 W
df 2 df 2 ⎟
⎟
Jacobian ⎜ df
⎜ 3
W
⎜ dξ1
⎝ dξ1
dξ 2
df 3
dξ 2
dT ⎟
df 3 ⎟
dT ⎠
⎟
Matrix
d
(δ z ) = M (δ z )
dt
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CO + H 2O R CO2 + H 2 + Q
toxic heat
1
doesn’t occur if equilibrium limited
X w/ catalyst
equilibrium
original
rxn
T
Figure 3. Conversion (X) versus Temperature (T).
Data Collection:
Products,
. I N
Reactants Reactor Unreacted Stuff,
Byproducts
V E
CoT ,τ
Figure 4. Schematic of a general reactor.
S S
.B
W make plots
r(conc,T)
ouput-input
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∫ r dxdydz
→ rV if homogeneous
dV
“well-stirred” reactor
(slow reactions)
“no” conversion
(really ~.1% conversion)
C = C0 ± .1% Æ can measure (output-input)
(r barely changes)
*need very sensitive product detection
“differential reactor”
From data:
guess mechanism
vary ( k , k eq )Æmake a fit
. I N
V E
S S
.B
W
W
W
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This lecture covers: theory of the chemostat, fed batch or semi-continuous fermentor
operations
[S]0 F
[S], x
V
F
. I N
F = Volumetric flow rate
x=
biomass
volume
V E
S S
[S]0 = Concentration of growth limiting substrate. (for growing cells)
μ=D
Biological Mechanical
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
0 at steady-state
1
F [ S ]0 − F [ S ] − μx V = 0
Yx
s
Divide by V
. I N
D ([ S ]0 − [S]) =
Yx
μx
V E
change in sugar
concentration
μ=D
s
S S
.B
At steady-state
x = Yx ([ S ]0 − [S])
s
W
What is the value of
W
[S] ? What more information do we need?
μ = f ([S])
W
Å must choose a growth model to connect μ and [S]
μmax [ S ] μmax [ S ]
μ= Æ at steady-state Æ D=
K s + [S ] K s + [S ]
Ks D
[S ] = substitute in x equation
μmax − D
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[DD Month YYYY].
⎛ Ks D ⎞
x = Yx ⎜ [ S ]0 − ⎟
s ⎝ μmax − D ⎠
μmax − D can go to 0. If you turn knobs incorrectly: if D is too high, the cells cannot
grow fast enough to reach steady-state. Washout will occur.
μmax [ S ]0
Dmax =
K s + [ S ]0
. I N
x, S S
V E
mass
volume
S
x
S
.B washout
D
W Dmax
W
Figure 2. Biomass/volume versus dilution rate. Beyond the maximum dilution rate,
washout occurs.
W
For real systems K s << [ S ]0 . Most cell growth systems reach maximum at fairly low
concentrations; hence x is flat, then drops off sharply.
dx
optimize x with respect to D? D=0 (no, because this would be batch reactor)
dD
biomass
Define productivity as = xD
(reactor volume )( time )
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d ( xD)
= 0 for optimum. (is a maximum)
dD
x xD
D D
Doptimum
K s << [ S ]0
. I N
Doptimum ≈ μ max
V E
≈ Dmax
S S
.B
Close to washout conditions.
Operability would be difficult. We would not want to run too close to washout
conditions.
W
W
Fed-batch fermentor (microbes or mammalian cells)
-used to achieve very high cell densities (e.g. hundreds of grams cell dry weight
(c.d.w)/liter)
W
If you want x final =
100 g
L
200 g wt
If Yx ≈ 0.5 , [S]0 = ≈ 20% Å Toxic, sugar content cells will die
s
L volume
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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[S]0 F
x(t)
S(t), very small
There is a dilution term, because as we feed in fresh medium, volume will change.
Volume often doubles.
x V = x0 V0 e μt
μ x0 V0 e μt
F[S ] =
Feed
0 Yx
sugar feed
s
sugar consumed
. I N
F=
x0 V0
[ S ]0 Yx
μ e μt
V E
s
Exponential flow rate. Typically μ
S S
specified as “small.”
Dilution:
dV
=F .B
dt
W
⎛
⎜
V(t ) = V0 ⎜1 +
x0
(
⎞
⎟
e μt − 1) ⎟ W
⎜ [ S ]0 Yx
⎝ s W ⎟
⎠
biomass x0 e μt
x= =
V 1+
x0
Yx [ S ]0
( e μt − 1)
s
μt
x0 V0 e
=
V
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“Logistic equation”
1)
1 dP
x dt
= αμ
product
growth associated (e.g. ethanol)
. I N
P≡
1 dP
volume
V E
2)
x dt
=β
t
P = β ∫ xdt
S S
not growth associated (e.g. antibiotics, proteins, antibodies)
.B
W
W
W
Cite as: K. Dane Wittrup, course materials for 10.37 Chemical and Biological Reaction Engineering, Spring
2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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This lecture covers : Significance, typical values and diffusion limit, approach to
equilibriu, and multivalency
Noncovalent Interactions
S S
.B
C p CL koff
= = Kd
Cc kon
L
mol s W
W
W
In general, for protein-protein interactions,
koff
Kd τ1 2 types
mM milliseconds non-specific stickiness
stronger
μM (micromolar) milliseconds-seconds cell surface, multi valent
interactions
nM minutes-hours antibodies, enzymes
pM hours-weeks growth factors
fM (femtomolar) weeks-months hycholase inhibitors
Cc Cc
Fractional saturation Y = =
C p , o Cc + C p
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
C p CL CL
Kd = →Y =
Cc CL + K d
Kd
CL log CL
If C p ,o ≈ CL ,o , then at equilibrium, CL ≠ CL ,o
Y=
CL ,o − yC p ,o
CL ,o − yC p ,o + K d
. I N
Y=
K d + CL,o + C p ,o − ( K d + CL,o + C p ,o ) 2 − 4C p ,o CL,o
V E
2C p ,o
S S
.B
If instead CL ,o C p ,o , CL ≈ CL,o
CL ,o
Y=
CL ,o + K d
W
W
How quickly is equilibrium reached?
dCc
dt W
= konCLC p − koff Cc
If CL , o C p , o “pseudo-1st order”
konCL = konCL ,o
C p ,o = C p + Cc
(complexed)
C p = C p ,o − Cc
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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dCc
= konCL,oC p − koff Cc = konCL ,o (C p,o − Cc ) − koff Cc
dt
= kon C p,oCL ,o − (konCL,o + koff )Cc
CL ,o
⇒ Cc (t ) = C p,o (1− e −kobs t )
CL ,o + K d
kobs = konCL,o + koff
ln 2
= half-time for reaching equilibrium
kobs
Cc
equlibrium
. I N
ln 2
kobs
t
V E
times.
S S
Figure 3. Concentration of complex versus time. Equilibrium is approached at long
Biosensor
.B
Surface plasmon resonance (label-free)
W
flow
W thin gold film
W hν
amount of reflected light is a
function of complex formation
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
Kd
signal
kon koff
koff
t
flow stop
signal signal
association dissociation
equilibrium
phase
V E kon
squares)
S S
best approach: fit one set of parameters to three phases of experiment. (global least
Multivalency (Avidity) .B
cell W
cell cell
W
W
cell
surface multivalent
label
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
free bound
detected same
. I N
V E
S S
.B
W
W
W
Cite as: K. Dane Wittrup, course materials for 10.37 Chemical and Biological Reaction Engineering, Spring
2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
moles mRNA
CmRNA ≡
cell volume
Kr ≡
mol mRNA
( time )( cell volume )
. I N
, transcription (function of gene dosage, inducers, etc.)
Vi ≡
cell volume
V E
vessel volume
d ( CmRNA Vi ) S S
dt
= K r Vi − γ r CmRNA Vi
.B
W
γ r ≡ first order rate constant for mRNA degredation
W
Vi ≡ a function of time (cells grow, divide)
Æ can’t pull out of the derivative
d Vi
W
Do the chain rule:
dC
CmRNA + Vi mRNA = K r Vi − γ r CmRNA Vi
dt dt
dCmRNA 1 d Vi
= K r − γ r CmRNA − CmRNA
dt Vi dt
1 d Vi
simplify: =μ (specific growth rate in exponential growth)
Vi dt
dCmRNA
= K r − γ r CmRNA − μ CmRNA
dt
dCmRNA
= K r − (γ r + μ )CmRNA
dt
at steady-state:
Kr
CmRNA, SS =
(γ r + μ )
Kr ⎛ − ( μ +γ r ) t ⎞
CmRNA = ⎜1 − e ⎟
(γ r + μ ) ⎝ ⎠
independent of the transcription rate constant K r
S.S.
. I N
CmRNA
V E
1
γr + μ
t
S S
.B
Figure 1. Concentration of CmRNA versus time. At long times steady state is
approached.
dC p
dt W
= K p CmRNA − (γ p + μ )C p
(1 − e−(γ r + μ )t ) − (γ p + μ )C p
dC p Kr
= Kp
dt (γ r + μ )
d
steady-state: =0, t →∞
dt
Kr K p
C p , SS =
(γ r + μ )(γ p + μ )
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 15
Prof. K. Dane Wittrup Page 2 of 4
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
C p , SS Kp
= Note: K p , γ p vary from protein to protein and condition
CmRNA, SS γp +μ
to condition
dC p
Integrate :
dt
⎛ (γ r + μ )e − (γ p + μ )t − (γ p + μ )e − (γ r + μ )t ⎞
C p = C p , SS ⎜ 1 + ⎟
⎜ γ p −γr ⎟
⎝ ⎠
Usually, γp γr
ln 2
in E. coli ∼ 7 minutes on average.
γr
ln 2
for most proteins, ∼ hours to days.
γp
also, γr μ
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
Cp
t
1
Delay is generally small compared to
γp +μ
Figure 2. Concentration of protein versus time.
Cellular compartmentalization
C p, 1 → C p,2 where
. I N
C p, 1 ≡ C p for compartment 1, and C p, 2 ≡ C p for compartment 2
rate = K transport C p,1
V E
S S
+ kon
koff
.B
rec. W
prod.
W
c y ut.
W
.
to
o
endocytosis cell
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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This lecture covers: Inorganic and enzyme catalysis and their properties; kinetics of
heterogeneous catalytic reactions; adsorption isotherms, derivation of rate laws; and
Langumuir-Hinshelwood kinetics
B
A
Product
. I N
Temperature drastically increases reaction rate.
Hot
V E
C2H6 Rxn occurs
S S
Fire
Figure 2. Schematic of tube reactor.
.B
W
Catalyst dramatically increases reaction rate.
W
A
W catalyst
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transition state
E
products
~Ea
reactants
rxn coordinate
rate constant:
k BT ⎡ (G − Greactants ) ⎤
k= exp ⎢ − ts ⎥
h ⎣ RT ⎦
G = H − TS
e − G / RT = e− H / RT e S / R
. I N
E
no catalyst
V E
S S
.B
with catalyst
W
rxn coordinate
W
Figure 5. Reaction diagram with and without catalyst.
intermediates.
Acid/Base catalysis
W
The reaction forms many intermediates. A catalyst lowers the energy of these
ROR + H 2O → 2ROH
k1 H
ROR + H ⊕ ROR
k−1 ⊕
H k2
ROR → ROH + R ⊕
⊕
k3
R ⊕ + H 2O → ROH + H ⊕
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H
QSSA ROR , R ⊕
⊕
⎡ H ⎤
d ⎢ ROR ⎥
⎦ = k ⎡ H + ⎤ ROR − (k + k ) ⎡ ROR ⎤
⊕ H
O≈ ⎣ 1⎣ ⎦ [ ] −1 2 ⎢ ⎥
dt ⎣ ⊕ ⎦
⎡ H ⎤ k1
⎢ ROR ⎥ = ⎡⎣ H + ⎤⎦ [ ROR ]
⎣ ⊕
⎦ QSSA k −1 + k 2
d [ ROH ] ⎡ H ⎤
= 2k2 ⎢ ROR ⎥
dt ⎣ ⊕ ⎦ QSSA
d [ ROH ] 2k1k2
≈ ⎡⎣ H + ⎤⎦ [ ROR ] = r
dt k−1 + k2
rA ∼ [ A]
rA ∼ [ catalyst ] (where ∼ denotes “proportional to”)
. I N
⎡ H ⎤
⎣
⊕
⎦
N +
⎡⎣ H + ⎤⎦ + ⎢ R O R ⎥ + ⎡⎣ R + ⎤⎦ = H added = ⎡⎣ H + ⎤⎦
V added
V E
⎛ k [ ROR ]
⎡⎣ H + ⎦⎤ ⎜1 + 1
⎜ k1 + k2
+
k1k2 [ ROR ] ⎞
⎟
⎟
k3 (k−1 + k2 ) [ H 2O ] ⎠
S= ⎣⎡ H + ⎦⎤ S
.B
added
⎝
keff [ ROR ] ⎡⎣ H + ⎤⎦
r=
1+ k [ ROR ]
added
W
r=
k [ catalyst ] [ A]
W
1+ k A [ A] + k B [ B ] + ...
W
All the things that the
catalyst binds to
Eley-Rideal: one reagent binds, 2nd reagent reacts with bound form
dN A
= VrA
f ([ A] , ⎡⎣ H ⎤⎦ )
+
dt
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 16
Prof. William H. Green Page 3 of 4
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moles
dN A
= ( area of metal ) rA′′ area s
dt
f (θ A )
N A bound
where θA =
N total sites
on surface
. I N
V E
S S
.B
W
W
W
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This lecture covers: External diffusion effects, non-porous packed beds and
monoliths, and immobilized cells
( x, y,z ) =
Ci fluid
Ni
Volume
N j on surface
. I N
θ surface
j ( x, y ) =
N sites on surface
∑ θ j + θvacancy = 1 V E
ri fluid
=
N rxn fluid
∑
⎛ A⎞
ν i ,n rn (C ) + ⎜ ⎟
N rxn suface
∑ ν r (C ,θ )
"
S S
.B
i ,m m
n =1 ⎝V ⎠ m =1
mol
s ⋅ vol W mol
s ⋅ area
QSSA for surface species: rj =
W "
∑ν r (C ,θ ) ≈ 0
"
j ,m m
dθ j
W
⎛ area ⎞
θQSSA = f (C ) At surface
= ( flows ) + rj" ⎜
0
⎟ N avagadro
dt ⎝ N sites ⎠
A
A P
δ
surface
Catalyst
S S
4. No reaction in the fluid
0=D
∂ 2C A
.B
∂z 2
WA = −rA'' W
−D
dC A
W
= − rA'' ( C z =0 ) (z=0 at the surface)
dz z =0
W ⎡ C main − C A ( z = 0) ⎤
C A ( z ) = C A ( z = 0) + ⎢ A
⎣ δ
z⎥
⎦
main
− C A ( z = 0)
= −rA'' ( C A, z =0 )
dC C
D A =D A
dz z =0 δ
Slow chemistry limit: C A ( z = 0) ≈ C Amain
(
rA'' ≈ rA'' C Amain )
Fast chemistry limit: C A ( z = 0) ≈ 0
D
C Amain ≈ rA''
δ
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 17
Prof. William H. Green Page 2 of 3
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D
= kc “mass transfer coefficient”
δ
kc d p
Sh = ÅSherwood number (dimensionless)
D
For spherical, catalyst particle with diameter dp:
Sh = 2 + 0.6 Re1 2 Sc1 3
υ ud μ
Sc = Re = p υ =
D υ ρ
. I N
V E
S S
.B
W
W
W
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external
transport
mass
transfer
coefficient rate law
observed rxn rate
intraparticle
=f(reactant concentration
diffusion
and product)
adsorption desorption
solid
sites rxn
Michaelis-
Menton ↔
W Langmuir-Hinshelwood
Haugen-Watson
enzyme kinetics
(Briggs-Haldane, Henri)
W kinetics
Logic: W
• list rxns
• hypothesize rate-limiting step
• derive rate law
• check for consistency w/ rate data
kA kS kD
A R AS R BS + C R S + B + C
k− A k− S k− D
product
S ≡ site on catalyst
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rAd = k A PACS − k− AC AS
kA
KA =
k− A
⎛ C ⎞
rAd = k A ⎜ PACS − AS ⎟
⎝
⎛
KA ⎠
PC ⎞
Similarly, rS = k S ⎜ C AS − C BS ⎟
. I N
⎛
⎝
PC ⎞
KS ⎠
rD = k D ⎜ CBS − B S ⎟ Æ K B =
1
V E
rD = k D ( CBS − K B PB CS )
⎝ KD ⎠ KD
Æ
S S
At steady-state,
.B
rAd = rS = rD (or else you would accumulate molecules)
W ki k j kl
W
Hypothesize, that adsorption is rate-limiting:
rA
kA
r r
S , D ≈0
kS k D
rS PC C P
≈ 0 ⇒ C AS − C BS ⇒ C AS ≈ BS C
kS KS KS
rD
≈ 0 ⇒ CBS − K B PB CS ⇒ CBS ≈ K B PB CS
kD
K PC P
Æ C AS ≈ B B S C
KS
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⎛ C ⎞
rAd = k A ⎜ PACS − AS ⎟
⎝ KA ⎠
⎛ KB ⎞
= k A ⎜ PACS − PB PC CS ⎟
⎝ KS K A ⎠
⎛ KB ⎞
= k ACS ⎜ PA − PB PC ⎟
⎝ KS K A ⎠
KB
C S0 = C S + PB PC CS + K B PB CS
KS
⎛ K ⎞
= CS ⎜1 + B PB PC + K B PB ⎟
⎝ KS ⎠
S S
Surface reaction is rate-limiting:
⎛ PP ⎞ .B
− rA =
k S CS0 K A ⎜ PA − B C ⎟
⎝ KC ⎠
W
W
1 + PB K B + PA K A
− rA =
W
Desorption is rate-limiting:
⎛ PP ⎞
k D CS0 K S K A ⎜ PA − B C ⎟
⎝ KC ⎠
PC + PA K A K S + K A PC PA
K AKS
Initial rate expirements, approximate − rA = f ( PA ) , PB ≈ PC ≈ 0 , K C = .
KB
Adsorption limit:
− rA = k ACS0 PAo
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 18
Prof. K. Dane Wittrup Page 3 of 4
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− rA
PAo
Figure 2. Reaction rate vs. initial partial pressure of A for the absorption limiting
case.
kS CS0 K A PAo
− rA =
1 + K A PAo
− rA
. I N
V E
PAo
S S
Figure 3. Reaction rate vs. initial partial pressure of A for the surface reaction
.B
limiting case.
Desorption limit:
W
− rA = k D CS0
W
− rA
W
PAo
Figure 4. Reaction rate vs. initial partial pressure of A for the desorption limiting
case.
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μ
X X X
X
X
X
X
X
X
X
critical value ≈ 0.01 mM
. I N
D.O.
V E
Figure 1. μ vs dissolved oxygen.
cell
1 2 3
Figure 2. Oxygen pathway.
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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at equilibrium
mol
3) O2 flux = kl (CO2 − CO2 ) [=]
*
area time
β
⎛P⎞
N
α
kl a = constantU s ⎜ ⎟ where Us is the superficial gas velocity
kl a[=] ⎜ ⎟⎜
⎝V ⎠
⎛ length ⎞ ⎛ area ⎞
⎟ = time
⎝ time ⎠ ⎝ volume ⎠
−1
(s-1)
E . I
U S [ =]
length
time
S V
(m/s)
P
=
power
V volume
.B S (W/m3)
const. = 0.002
α = 0.2
W
β = 0.7
W
W
@ SS, O2 transport = O2 uptake by biomass
kl a (C − CO2 ) =
* μX
biomass growth rate
or
dX
O2 dt
YX O
2
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O2 transport in tissues
o
o R0
r
o o
o
capillary radius Rc
DO2 ∂ ⎛ ∂CO2 ⎞
⎜r ⎟ = VO2
r ∂r ⎝ ∂r ⎠
metabolic consumption rate of
N
Fick's Law
oxygen, zero-order
(cylindrical coordinates)
E . I
Boundary conditions:
S V
symmetry
no-flux
flux=0 @ r=R0
.B S
∂CO2
DO2
∂r
= 0 @ r=R0
W
CO2 = CO2 , plasma @ r=Rc
W
Integrate twice:
CO2
W⎛ r* ⎞
= 1 + Φ ⎜ r *2 − R*2 − 2 ln * ⎟
CO2 , plasma ⎝ R ⎠
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1
CO2
Φ decreasing
CO2 , plasma
r*
When R ≈ 0.05,
*
CO2 = 0 @ r * = 1 when Φ ≥ 0.2
~50-100 μm
. I N
o
O2
V E
S S
.B
necrotic core
W
W
W
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
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This lecture covers: Effective diffusivity, internal and overall effectiveness factor,
Thiele modulus, and apparent reaction rates
R
r
. I N
[S]0= surface concentration of a growth
substrate (ex. glucose and O2)
V E
Figure 1. Sphere of Cells
S S
d [S ] .B
Assume pseudo-homogeneous medium and Fick’s Law describes diffusion
length 2
W
# molecules
Flux = − D , where Flux [=] and D [=]
dr area ⋅ time time
− rs = knCsn
W
V C
− rs = max s
W
K s + Cs
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-rs
n=1
n=0
Cs
. I N
In some cases, S still hasn’t
E
penetrated to the center
V
S S
t=0 Æ .B tÆ ∞
W
W
Figure 3. Time progression as species, S, enters the sphere
Flux ⋅ 4π r 2
W
Thin shell r to (r+Δr)
Sin by diffusion –Sout by diffusion –Scons by reaction=0
r + Δr
− Flux ⋅ 4π r 2 − kn Csn 4π r 2 Δr = 0
r
Divide through by 4πΔr and take the limit as ΔrÆ0
(
d Flux ⋅ r 2 ) −k C r n 2
=0
n s
dr
d ⎛ dC ⎞
⎜ − D s ⋅ r 2 ⎟ − knCsn r 2 = 0
dr ⎝ dr ⎠
d 2Cs 2 dCs kn n ⎫
2
+ − Cs = 0 ⎬ 2nd order ODE
dr r dr D ⎭
2 Boundary conditions:
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 20
Prof. K. Dane Wittrup Page 2 of 5
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Cs r=R
= Cs ,0
Cs is finite everywhere, or
dCs
=0
dr r =0
Nondimensionalize
r C
ρ= S= s
R Cs ,0
d 2 S 2 dS
+ − φ 2S n = 0
dρ2 ρ dρ
Boundary conditions: S=1 @ ρ=1
S is finite everywhere
φ =
2 kn R 2Csn,0−1
=
(R 2
D ) =
characteristic diffusion time
D (1 k C ) n −1
characteristic reaction time
n s ,0
W
Figure 4. Reaction and diffusion limited regimes
1 sinh(φρ )
S=
ρ sinh(φ )
e z − e− z
sinh( z ) =
2
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[DD Month YYYY].
1
φ = 0.1
S
φ =1
φ↑
φ = 10
ρ
1
= 4π RDCs ,0
dS
dρ
= 4π RDCs ,0 (φ coth φ − 1)
. I N
E
ρ =1
3
η= (φ coth φ − 1)
φ2
S V
η
1
.B S
0.1
W η∝
1
0.01
W φ
.01
W 0.1 1
φ
10 100
*For a variety of reaction kinetics, geometries and rate laws, plots of η vs φ all look
the same.
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
. I N
V E
S S
.B
W
W
W
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2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on
[DD Month YYYY].
A products
. I N
V E
Deff (actual is very complicated)
S S
Void Fraction φ ~.5
.B
C A ( x j , ym , zl )
W
j = 1,30
m = 1,30 W
l = 1,30
(points) W
(11-21) Di ∇ 2Ci − U ⋅∇Ci + ri fluid = 0 Å in the fluid i=1, N species
fluid
∂Ci
Di + ri surface = 0 (boundary condition for the above)
∂nˆ surface
Ergun’s Eq.:
dP G 1−φ ⎡150 (1 − φ ) μ ⎤
(4-22) =− ⎢ + 1.75G ⎥
dz ρ gc Dp φ 3 ⎢⎣ Dp ⎥⎦
G
where P = ρ RT , ρU z =
A
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∂FA
= ArAeff rAeff = (effectiveness factor )rAC Ab ( z )
∂z
area ( )
Ω C Ab ( z ) (or η internal)
total
∂Fi mol
= Ari eff = AΩri ideal ri ideal [=]
∂z vol. s
ri = ri′ ρc (1 − φ )
⎛ surface area of cat. ⎞
. I N
= ri′′ ⎜
⎝ wt. cat.
⎟ ρ c (1 − φ )
⎠
V E
m2
ac / m particle
S
[=] Sa + (macroscopic surface area, visual) S
.B
g
1 dFA
A dz W
= +U
dC A
dz
− Da
d 2C A
dz 2
hope this is 0!
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( )
kc ac C Ab − C As = η ( C As ) rA particle ( C As ) V p
∂ 2C A
Dinside + rA ( C A (r ) ) = 0
∂r 2
∂C A ∂C A
∂r r =0
=0 Deff inside
∂r
(
= kc C Ab − C As )
∂C A
kc C A r = R + Deff inside = kc C A bulk
∂r r=R
Matlab:
1) Guess C As ( C A surface)
∂C A
2) Use boundary conditions to get corresponding
∂r r=R
3) Solve ODE (ode15s)
∂C A
4) Vary guess ( C As ) to make
∂r
= 0 at center
. I N
st
1 oder irrev.
η 3
V E
Ω=
1+
η k1′′ Sa ρb
η=
S φ12
S
(φ1 coth(φi ) − 1)
.B
kc ac
φ1 = … k1′′
W
W
W
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dFi
= Ari eff
dz
z=0 z=L
V E
BL: δ
S S
.B
porous
catalyst
W
W
particle
W
dp
Biot Number:
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kc d p D fluid
Bim = where kc ∼
eff
Dinside δ
D diameter
Bim = efffluid
Dinside δ
Mears’ Test:
rA′ (observed) ρb R p n
if < 0.15 where n ≡ order of rxn
kc C A bulk
Similarly,
. I N
< 0.15 then Tb ≈ Ts (text: Eqn. 12-63)
V E
Weisz-Prater:
[>]
S S
rA′ (observed) ρc R p 2
.B
if eff
Dinside C A bulk
W 1 (text: Eqn. 12-61)
W
then you can neglect internal diffusion limitations, i.e. C As ≈ C Ab ≈ C A ( r = 0)
η
1000
100
W β = 0.6
Ea ∼ 30 RTs
ΔH rxn 0⎫
⎬ temp. dep. & exothermic
10
Ea 0 ⎭
1
.1 1 10 100 φ1
.1
ΔH rxn = 0
or Ea = 0
ΔH rxn > 0
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ktTs
⎛ ∂Ci ⎞
kc ( Ci ,b − Ci , s ) = − Dinside
eff
⎜ ⎟
⎝ ∂r ⎠ r = R
= ∫ ri dV .
⎛ ∂Ci ⎞
kc Ci − Dinside
eff
⎜ r ⎟ = kc Ci , bulk
⎝ ∂ ⎠ r =R
r=R
⎛ ∂Ci ⎞
⎜ r ⎟ =0
⎝ ∂ ⎠ r =0
rA ≈ −k C A
e − Ea RT
. I N
rAeff ≈ f (k ) C A
V E
fit to: Aeff e− Ea
eff
RT
. (text: Table 12-1)
S S
.B
W
W
W
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Review
Fundamental Equations:
∂nm
= Fm ,o − Fm ,out + ∫∫∫ rm ( x, y, z , t ) dxdydz
∂t
infinitesimal volume
∂Cm
= ∇ ⋅ Fm + rm
∂t
K eq = e−ΔGrxn RT
( K eq is unitless)
. I N
N products
∏ ⎛ Pm
⎜ 1 bar ⎟
⎝
⎞
⎠
νn
V E
K eq = m =1
reactants
∏j =1 ⎝
⎛ Pj ⎞
⎜ 1 bar ⎟
⎠
−ν j
S S
k forward .B
Kc =
kreverse
W
H 2O2 → H 2 + O2 W
n
=
V RT
P
W
⎛ PH 2 ⎞⎛ PO2 ⎞
⎜ 1 bar ⎟⎜ 1 bar ⎟
K eq = ⎝ ⎠⎝ ⎠
⎛ PH 2O2 ⎞
⎜ 1 bar ⎟⎠
⎝
Kc =
[ H 2 ][O2 ]
[ H 2O2 ]
mol
units K c [ =]
L
Convection dominated:
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∂P G 1 − φ ⎡150 (1 − φ ) μ ⎤
Ergun Equation: =− 3 ⎢
+ 1.75G ⎥
∂z pg c D p φ ⎣⎢ Dp ⎦⎥
∂U cvtot ∂V
+ P cv = ∑ Fj H j + Q + Ws ( U cv depends on T)
tot
∂t ∂t
Special Cases:
. I N
Perfectly Homogeneous (“well stirred”, “perfectly mixed”)
S S
.B
Æ CSTR, no t-dependence
0 = Fin − Fout + r ( Cout )
W
Homogeneous in x,y, not in z (no t-dependence)
W
PFR (typically gives higher productivity than CSTR)
∂Fm
∂z
“sort of” PFR
∂Fm
W
= Arm ( C ( z ) )
•
cat
bubble •
Figure 1. a) mass transfer from gas to liquid b) mass transfer into catalyst particle
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 25
Prof. William H. Green Page 2 of 3
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∂ 2Cm ⎛ 2 ⎞ ∂Cm
D +⎜ ⎟ + rm ( C ( r ) ) = 0
∂r 2 ⎝ r ⎠ ∂r
- nondimensionalize
- some solutions in book
- (18.03)
Thiele modulus
rm ( Csurface )
φ2 ≡
Dsolid Cm , s R 2
- if small (<1): reaction limited, ignore effectiveness factor Ω (internal diffusion
fast)
- if big: transport matters!
kL A Æ correlations
(sphere-packed bed)
S V
Finto
particle
= kc A(Cbulk − Cs )
.B S kc ∼
D
δ
Converting the second-order differential equation into first-order ordinary differential
equations for MatLab solvers:
∂Cm W
∂r
= qm
W
D W
∂qm 2
+ qm + rm = 0
∂r r
2
∂qm − qm + rm
Æ = r Æ MATLAB: ode15s
∂r D
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See page 781 of the 4th edition for the external transport limited PBR derivation (no axial
diffusion or radial dispersion).
where U is the superficial molar average velocity. This is defined as the velocity that the
fluid would have if no catalyst were present. It can also be thought of as the velocity that
would be measured immediately upstream or downstream of the packed bed.
This equation is incorrect if you consider the units, there should be an additional factor of
phi, the void volume, in it. The bulk concentration should be measured by taking a fluid
sample, not measuring the total amount of a component per unit volume of the entire
reactor.
FA[=]moles time
FA[≠ ]moles fluid volume × reactor volume time
. I N
E
The correct relationship is:
FA = C A,bulkϕUAc
S V
S
FA[=]moles time[=]moles fluid volume × fluid volume reactor volume×reactor volume time
.B
W
This is important for converting from the flowrate to the concentration correctly in a
PBR.
W
If you want to know the residence time in your PBR, the important velocity is the
W
ACTUAL average axial velocity of the fluid flowing in the void space, not the superficial
velocity. The reduction in reactor volume by incorporating catalyst causes the residence
time to be shorter than predictions using the superficial velocity. In cases where the fluid
is water (constant volumetric flow rate):
Vactual = U
ϕ
τ = LV
actual
A similar mistake with the superficial velocity is made on page 843. A simple remedy is
to replace U with Uφ in these equations.
Cite as: David Adrian, course materials for 10.37 Chemical and Biological Reaction
Engineering, Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute
of Technology. Downloaded on [DD Month YYYY].
Four runs were completed during the two recitations on Monday, March 19, 2007.
The settings for the four runs are given below:
The baseline intensity before we started run 1 was I0 = 2977 ± 4, the stirrer was
V E
The data from the four experiments are tabulated in .txt files and are posted on the
10.37 Stellar webpage. In each file, the first column is the time (sec) and the
second column is -ln(I/I0).
S S
.B
The four data sets have been fit to the model:
I
W
− ln = A + B exp(− Ct )
I 0
W
The parameter values for A, B and C are tabulated below. In addition, figures
showing the experimental data and the fit model for each run are included at the
W
end of this assignment.
Run A B C (sec-1)
1 2.76 -2.25 .0018
2 2.00 0.56 .0016
3 1.05 0.97 .0019
4 0.44 0.60 .0027
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1) Do the values of α, β, k1, and k2 that you obtained in the pre-lab provide semi-
quantitative agreement with the data measured during recitation? How far off are
the predictions that you would make using the model and parameters suggested
from the pre-lab information? What could you do to get better predicted
parameters?
2) Can you determine the conversion in the experiment we did on Monday from
the dataset? Would it be helpful to know the value of "b" that relates ln(I/I0) to the
concentrations? Explain.
3) From the noise level in the baseline, how close would one expect the agreement
to be if the model were perfect and the parameters α, β, k1, and k2, and V and flow
rates were all known perfectly?
. I N
V E
S S
.B
W
W
W
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. I N
V E
S S
.B
W
W
W
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. I N
V E
S S
.B
W
W
W
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Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology. Downloaded on [DD Month YYYY].
Note: Parts A – D should be completed before the Weblab on Monday, March 19, 2007,
but don’t have to be turned in until April 6, 2007.
Introduction
This exercise concerns the reaction of phenolphthalein (PHEN) in an aqueous solution of
sodium hydroxide:
Reaction (1) can be assumed to occur rapidly, so the rate determining step is reaction (2).
The rate laws for reaction (2) are:
r1 = k1[PHEN2-][OH-]
r2 = k2[PHENOH ] 3-
(3)
(4) . I N
V E
S S
The purpose of this exercise is to determine the reaction constants for this reaction, and to
predict the operating conditions required to achieve a given conversion of PHEN2- to
PHENOH3- in a non-ideal reactor. You will test your predictions by running experiments
on the reactor in question.
.B
PART A
W
http://weblabs.cheng.cam.ac.uk/reactors_batchdata.html contains experimental data from
W
reactions (1) and (2) carried out in a batch reactor. To track the progress of the reaction, a
spectrophotometer has been used to measure the intensity of light (550 nm) transmitted
W
through the reaction solution. This intensity, I, is related to the concentration, c, by the
Beer-Lambert law:
c = –b * ln (I/I0) (5)
Note: As concentration increases (more pink stuff), the intensity of light passing through
the sample decreases (c up, I down). b is positive, but knowing the value is unnecessary
because it will cancel out.
Show that the time variation of the intensity, I, through the experiment can be expressed
as: (give an expression for the pseudo first order rate constant k1’)
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ln (I ) − ln (I t=∞ )
ln (I t=0 ) − ln (I t=∞ )
[
= exp − (k1' + k 2 )t ] (6)
Use the experimental data to determine the rate constants k1 and k2 for the first set
of data (collected at 20.0 °C). The above data was taken in an IDEAL BATCH
REACTOR, unlike Part B and beyond.
Part B
The reaction is to be carried out in a continuous reactor (CSTR - Figure 1). More
information on the reactor setup can be found at
http://weblabs.cheng.cam.ac.uk/reactors.html. The available reactant concentrations are:
NaOH: [OH-]in = 0.20 mol/l
Phenolphthalein: [PHEN]in = 7.2 x 10-5 mol/l
NaOH
Q1
.Q
I N
Phenolphthalein
Q2
V
VE Products
S
Figure 1: A schematic of the reactor S
.B
W
In most cases, modeling a reactor as a stirred tank is not sufficiently accurate. One model
for a non-ideal reactor is the bypass/dead volume model, in which a fraction β of the flow
W
bypasses the reaction zone, and only a fraction α of the reactor volume is utilized. This is
shown schematically in figure 2.
W βQ
Q αV
(1–β)Q
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c(t )
CSTR: = e −t / τ , (7)
N t /V
c(t ) (1 − β ) exp − 1 − β t ,
2
Bypass/Dead volume: = βδ (t )τ + (8)
N t /V α ατ
where τ = V / Q .
Part C
Use the experimental data at http://weblabs.cheng.cam.ac.uk/reactors_tracerdata.html to
determine α and β for the bypass/dead volume model when applied to the reactor in non-
ideal setup. Note: Data is given for the reactor when run as close to being a perfect
I N
CSTR as possible, as well as when it is run as a non-ideal CSTR. The perfect CSTR data
.
will allow you to relate I (t=0) to I0, which is just a reference value. I (t=0) is the intensity
directly AFTER the pulse is given, when the concentration is Nt / V.
V E
Part D
S S
It is desired to run the reactor at a product flowrate, Q, of 25 ml/min and a conversion, X,
.B
of 30 %. In this case, conversion is defined as:
[ΡΗΕΝΟΗ 3− ]
X =
W
[ΡΗΕΝ 2− ] + [ΡΗΕΝΟΗ 3− ]
, (9)
W
to avoid any ambiguities due to dilution of the feed streams.
W
Assume that this reactor can be modeled as an ideal continuous stirred-tank reactor
(CSTR) of volume V = 250 ml. Use steady state material balances to show that to achieve
a product flowrate, Q, at conversion, X, the NaOH flowrate must be:
X Q(k 2V + Q )
Q1 = (10)
1 − X k1V[ΟΗ − ]in
Now assume that the reactor behaves according to the bypass/dead volume model. What
value of Q1 is required to give a product flowrate of 25 ml/min at a conversion of 30%?
In order to avoid too much unnecessary algebra, it may be useful to set up an Excel
spreadsheet (or similar) so that you can determine the conversions at different flowrates
with your calculated values of the parameters α and β.
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Part E
Experimental Procedure – this will be done as a group in recitation on Monday,
March 19, 2007
The aims of the experiment are:
1. To test the assumption that the reactor behaves as a CSTR.
2. To test the non-ideal model and parameters you have derived in your preliminary
analysis.
To determine a baseline reading for the intensity, set the flowrate of NaOH to the value
calculated from equation (10). Once a steady value for I0 is achieved, set the flowrate of
phenolphthalein to give a total flowrate of 25 ml/min.
Let the reactor equilibrate and record the steady state intensity.
Adjust the flowrates of the two reactants to the values calculated for the non-ideal reactor
setup. Again, let the reactor equilibrate and record the steady state intensity.
The plan is that each recitation will perform two runs, and you will analyze the data from
both recitations (up to four sets of data).
. I N
Part F
Experimental Data Analysis
V E
S S
Data analysis requirements will be posted on the 10.37 Stellar website after the Weblab is
completed, and will be due with the rest of the write-up on April 6, 2007.
.B
W
W
W
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In the first problem, Fogler 2-5, the textbook asks to use the figure to calculate the
conversions. However, the figure itself has problems such as not matching with the table
above it (less data points and one misrepresented point) and difficult to get accurate
results. You are required to use the values in the table instead of the figure and Matlab to
solve this problem. The use of matlab involves numerical interpolation (by command
interp1, together with a spline scheme to get a smooth interpolation), numerical
integration (quad), and numerical solution to equations (fzero). These will be also used in
the RTD problem. Of course, any method getting the accurate results will be accepted.
x0=fzero(@equation,1)
y=quad(@curve,0,1);%to integrate function curve(x) with x from 0 to 1
function y=curve(x)
data=[1 2 3 4 5;1.1 2.1 3.01 4.03 5.2]';
y=interp1(data(:,1),data(:,2),x,'spline');
return
. I N
function y=equation(x)
t=0.3;y=curve(x)*x-t;
return
V E
S S
In the problem of Fogler 6-6, plot the selectivities vs. concentrations using Matlab, not by
.B
crude sketching. This will help you in understanding the obscure problem
statement better.
W
W
W
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S S
.B
dN B
= 0 = −FB,out + kN A
dt
FB,out = kN A
dN C W
dt
W
= 0 = −FC ,out + 2kN A
W
FC ,out = 2kN A
Plugging in the three mole balance relationships into the
enthalpy balance we find:
dH A
− kN A H A + N A = Q& − kN A H B − 2kN A H C
dt
dH A
N A = Q& − kN A (H B + 2H C − H A ) = Q& − kN A ∆H rxn (T )
dt
dH A dT
= c
p,a
dt dt
Problem 1. Airbags contain a mixture of NaN3, NaNO3, and SiO2. When the vehicle is in
a crash, the following reactions are initiated:
2 NaN3 Æ 2 Na + 3 N2
10 Na + 2 NaNO3 Æ N2 + 6 Na2O
a) If 150 g of NaN3 are used in an airbag, how many grams of NaNO3 and SiO2 must be
included so that all of the sodium in the system can be safely sequestered as glass? Note
the sodium-containing compounds NaN3, Na, and Na2O are all dangerous and toxic.
b) The most important species for airbag performance in a crash are NaN3 and N2, so
there are two obvious definitions of conversion:
and
. I N
E
XN2 = (moles of N2)/(total moles of N2 when all reactions are completed).
V
they be?
S S
What units do XNaN3 and XN2 have? Does XNaN3 equal XN2? If not, how different could
.B
There are three other related quantities, ξ1, ξ2, and ξ3, the extents of reactions 1,2, and 3.
Note that each ξ has units of moles. Write algebraic equations for each X in terms of the
ξ‘s.
W
W
c) Suppose that reaction 1 has a rate expression r1=k1/V (this reaction proceeds at a
W
steady rate as a reaction front moves through the solid NaN3), reaction 2 has a rate
By the convention used in this course, all the r’s have units of moles/second/liter. Write
rN2, the rate of production of N2 per unit volume, in terms of r1, r2, and r3.
Write the equations for rate of change of the number of moles, dni/dt, for all the chemical
species (i=N2, NaN3, Na, NaNO3, Na2O, SiO2, glass).
d) Of course the volume of the airbag, V, is dramatically changing during the course of
the reaction due to the creation of a gas, N2, inside the bag. If the bag can expand fast
enough to so that the pressure inside the bag is similar to the pressure outside the bag, by
the ideal gas law one would expect:
V = Vo + VN * nN2
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and under this condition the bag would expand depending on the rate at which gas is
created:
dV/dt = VN * dnN2/dt
where VN is the molar volume of a gas at atmospheric pressure (~22 liter/mole) and nN2 is
the number of moles of N2 in the airbag. The initial volume of the airbag Vo ~70 cm3.
However there is a physical limit on how fast the airbag can expand. When an airbag is
expanded by gas pressure, the radius of the bag cannot grow faster than the speed of
pressure fronts in the gas, approximately the speed of sound:
so there is an upper bound on how fast the airbag can grow; for a spherical airbag:
dV/dt = 4π R2 dR/dt
so dV/dt < 4π (3V/4π)2/3 csound = (36πV2)1/3csound . I N
So a reasonable approach to model this numerically is
V E
if (V<Vo + VN*nN2)
S S
.B
dV/dt = (36πV2)1/3csound
else
dV/dt = VN * dnN2/dt
endif
W
W
Using a numerical ODE solver in Matlab, solve the coupled system of differential
equations for the n’s and V. Take k1~103 moles/s, k2~104 liter/mole-s, k3~105 liter/s.
W
Make and turn in a plot of XN2 vs. time, ξ3 vs. time and volume vs. time for the first 10
milliseconds of operation. Also, make and turn in a plot of volume vs. time for just the
first 0.1 milliseconds of operation. Does the volume vs. time behavior make physical
sense? If not, go back and modify your Matlab program to fix the non-physical dV/dt
behavior.
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Problem 2. One of the students in this class recently measured the reaction of vinyl
radical (C2H3) with ethene (C2H4), a reaction important in flames, pyrolysis, and
polymerization reactors. Vinyl radical absorbs purple light, so the amount of light
absorbed is proportional to the concentration of the vinyl radical. In each experiment the
student measured the time variation in the amount of purple light passing through his
constant volume sample using a photodetector. The voltage signal from the photodetector
is linearly related to the absorbance, which is proportional to [C2H3], so
where b is an uninteresting number related to how well the electronics baseline was
zeroed out before each experiment.
He performed similar experiments many times, each time with different initial
concentrations of ethene in the sample. From these experiments, he extracted the rate
constant “k” at various temperatures and pressures.
S
reaction to follow elementary-step kinetics, i.e. S
equilibrium is achieved the vinyl concentration is too small to detect). You expect this
-rC2H3=(k0 + k[C2H4])[C2H3]
.B
(Eq. 2)
W
k0 accounts for all other first-order loss processes of C2H3 in the experiment (e.g.
unimolecular reaction). Because the initial concentration of C2H3 is much smaller than
W
the concentration of C2H4, it is reasonable to assume that the concentration of C2H4 does
not vary significantly during each experiment. Therefore one expects a simple
W
exponential decay of [C2H3]:
a) Write out the algebraic relationship between τ and k. Fit the measured signal for the
nth experiment Sn to this form:
Give expressions for An, Bn, and τn in terms of b, m, [C2H3]o, k0, k, and [C2H4]0,n. Which
of the three fit parameters An, Bn, and τn depends on k and [C2H4]0 ?
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b) Use Matlab to plot 1/τn vs. [C2H4]n, where τn is the exponential decay time constant
determined by fitting the data from the nth experiment. How can you use this plot to
determine the rate constant “k”?
Your assignment is to compute the rate constant “k” for the reaction of interest from the
student’s data, contained in files vinylethene1, vinylethene2, and vinylethene3 on the
10.37 course website. In each file the first column is the time in seconds, and the second
column is the measured signal Sn. The first dataset is for [C2H4]=6.7x10-4 M, the second
for [C2H4]=4x10-4 M and the third for [C2H4]=1.33x10-4 M.
Turn in the value of “k” you derived from modeling the student’s experimental data
(don’t forget to specify the units of “k”!), and also turn in plots comparing your model
predictions using this “k” with the experimental data.
N.B. Notice that in this type of “pseudo-first-order” experiment, one can determine “k”
without knowing [C2H3]o, the calibration constant “m” relating the signal to [C2H3], what
. N
the products of the reaction are, nor what the competing reactions are (that contribute to
I
k0). Because of these simplifications, this type of experiment is very widely used to
determine rate constants.
V E
S S
.B
W
W
W
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Problem 1. Airbags contain a mixture of NaN3, NaNO3, and SiO2. When the vehicle is in a crash, the
2 NaN3 Æ 2 Na + 3 N2
10 Na + 2 NaNO3 Æ N2 + 6 Na2O
a) If 150 g of NaN3 are used in an airbag, how many grams of NaNO3 and SiO2 must be included so that all
of the sodium in the system can be safely sequestered as glass? Note the sodium-containing compounds
NaN3, Na, and Na2O are all dangerous and toxic.
b) The most important species for airbag performance in a crash are NaN3 and N2, so there are two obvious
definitions of conversion:
and
. I N
What units do XNaN3 and XN2 have? Does XNaN3 equal XN2? If not, how different could they be?
There are three other related quantities, ξ1, ξ2, and ξ3, the extents of reactions 1,2, and 3. Note that each ξ
has units of moles. Write algebraic equations for each X in terms of the ξ‘s.
V E
S
c) Suppose that reaction 1 has a rate expression r1=k1/V (this reaction proceeds at a steady rate as a reaction
front moves through the solid NaN3), reaction 2 has a rate expression r2=k2[Na][NaNO3], and reaction 3 has
a rate expression r3=k3[Na2O]/V.
S
.B
By the convention used in this course, all the r’s have units of moles/second/liter. Write rN2, the rate of
W
Write the equations for rate of change of the number of moles, dni/dt, for all the chemical species (i=N2,
W
NaN3, Na, NaNO3, Na2O, SiO2, glass).
W
d) Of course the volume of the airbag, V, is dramatically changing during the course of the reaction due to
the creation of a gas, N2, inside the bag. If the bag can expand fast enough to so that the pressure inside the
bag is similar to the pressure outside the bag, by the ideal gas law one would expect:
V = Vo + VN * nN2
and under this condition the bag would expand depending on the rate at which gas is created:
dV/dt = VN * dnN2/dt
where VN is the molar volume of a gas at atmospheric pressure (~22 liter/mole) and nN2 is the number of
moles of N2 in the airbag. The initial volume of the airbag Vo ~70 cm3.
However there is a physical limit on how fast the airbag can expand. When an airbag is expanded by gas
pressure, the radius of the bag cannot grow faster than the speed of pressure fronts in the gas,
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so there is an upper bound on how fast the airbag can grow; for a spherical airbag:
dV/dt = 4π R2 dR/dt
so dV/dt < 4π (3V/4π)2/3 csound = (36πV2)1/3csound
if (V<Vo + VN*nN2)
dV/dt = (36πV2)1/3csound
else
dV/dt = VN * dnN2/dt
endif
Using a numerical ODE solver in Matlab, solve the coupled system of differential equations for the n’s and
V. Take k1~103 moles/s, k2~106 liter/mole-s, k3~105 liter/s. Make and turn in a plot of XN2 vs. time, ξ3 vs.
time, and volume vs. time for the first 10 milliseconds of operation. Also, make and turn in a plot of
volume vs. time for just the first 0.1 milliseconds of operation. Does the volume vs. time behavior make
physical sense? If not, go back and modify your Matlab program to fix the non-physical dV/dt behavior.
Submit your Matlab program(s) to the 10.37 course website.
Problem 1 Solution
a)
→ NaN3 Æ Na + 3/2 N2. I N
(2 NaN3 Æ 2 Na + 3 N2)÷2
(10 Na + 2 NaNO3 Æ N2 + 6 Na2O)÷10
(Na2O + 10 SiO2 Æ glass)x6/10
VE
→ Na + 1/5 NaNO3 Æ 1/10N2 + 6/10 Na2O
→ 6/10Na2O + 6SiO2 Æ 6/10glass
.B
1mol
n NaN3 ,o = 150g = 2.3mol
65g
W
1mol NaNO3 2.3 85g
n NaNO3 ,o = n NaN 3 ,o ⋅ = mol = 0.46mol or m NaNO3 ,o = 0.46mol = 39g
5mol NaN 3 5 1mol
n SiO2 ,o = n NaN 3 ,o ⋅
6mol SiO2
1mol NaN 3
W
= 6 ⋅ 2.3mol = 13.8mol or mSiO2 ,o = 13.8mol
60g
1mol
= 830g
2ξ1
W
b) XNaN3 and XN2 are dimensionless. XNaN3 does not equal XN2 during the reaction.
nN2 3ξ1 + ξ 2
X NaN 3 = X N2 = =
n NaN 3 ,o nN2 , f 8
n NaN 3 ,
o
5
2ξ1 3ξ1 + ξ 2 ξ − 5ξ 2
X NaN 3 − X N 2 = − = 1
n NaN 3 ,o 8
n NaN 3 ,o 8n NaN 3 ,o
5
The difference between XNaN3 and XN2 will be determined by the kinetics of r1 and r2 (i.e.
the rate of change of ξ1 compared to ξ2).
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Species mol balance dni/dt (using extents) dni/dt (using reaction rates)
NaN3 nNaN3 = nNaN3,o - 2ξ1 dn NaN 3 dξ1 dn NaN 3
= −2 = −2r1V
dt dt dt
NaNO3 nNaNO3 = nNaNO3,o - 2ξ2 dn NaNO3 dξ dn NaNO
= −2 2 3
= − 2 r2V
dt dt dt
SiO2 nSiO2 = nSiO2,o - 10ξ3 dn SiO2 dξ 3 dn SiO 2
= −10 = − 10 r3V
dt dt dt
Na nNa = 2ξ1 - 10ξ2 dn Na dξ dξ dn Na
= 2 1 − 10 2 = (2r1 − 10r2 )V
dt dt dt dt
N2 nN2 = 3ξ1 + ξ2 dn N 2 dξ1 dξ 2 dn N 2
=3 + = (3r1 + r2 )V
dt dt dt dt
Na2O nNa2O = 6ξ2 − ξ3 dn Na2O dξ 2 dξ 3 dn Na2O
=6 − = (6r2 − r3 )V
dt dt dt dt
Glass nglass = ξ3
. I N dn glass
dt
= r3V
V E
d) See the Matlab solution provided. Plots showing XN2 vs. time, ξ3 vs. time, and
volume vs. time are copied below.
S S
.B
W
W
W
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Problem 2. One of the students in this class recently measured the reaction of vinyl radical (C2H3) with
ethene (C2H4), a reaction important in flames, pyrolysis, and polymerization reactors. Vinyl radical absorbs
purple light, so the amount of light absorbed is proportional to the concentration of the vinyl radical. In
each experiment the student measured the time variation in the amount of purple light passing through his
constant volume sample using a photodetector. The voltage signal from the photodetector is linearly related
to the absorbance, which is proportional to [C2H3], so
where b is an uninteresting number related to how well the electronics baseline was zeroed out before each
experiment.
He performed similar experiments many times, each time with different initial concentrations of ethene in
the sample. From these experiments, he extracted the rate constant “k” at various temps and pressures.
. I N
k0 accounts for all other first-order loss processes of C2H3 in the experiment (e.g. unimolecular reaction).
Because the initial concentration of C2H3 is much smaller than the concentration of C2H4, it is reasonable to
V E
assume that the concentration of C2H4 does not vary significantly during each experiment. Therefore one
S S
.B
a) Write out the algebraic relationship between τ and k. Fit the measured signal for the nth experiment Sn
to this form:
Sn(t) = Bn + An exp(-t/τn)
W
(Eq. 4)
W
Give expressions for An, Bn, and τn in terms of b, m, [C2H3]o, k0, k, and [C2H4]0,n. Which of the three fit
parameters An, Bn, and τn depends on k and [C2H4]0 ?
W
b) Use Matlab to plot 1/τn vs. [C2H4]n, where τn is the exponential decay time constant determined by
fitting the data from the nth experiment. How can you use this plot to determine the rate constant “k”?
Your assignment is to compute the rate constant “k” for the reaction of interest from the student’s data,
contained in files vinylethene1, vinylethene2, and vinylethene3 on the 10.37 course website. In each file the
first column is the time in seconds, and the second column is the measured signal Sn. The first dataset is for
[C2H4]=6.7x10-4 M, the second for [C2H4]=4x10-4 M and the third for [C2H4]=1.33x10-4 M.
Turn in the value of “k” you derived from modeling the student’s experimental data (don’t forget to specify
the units of “k”!), and also turn in plots comparing your model predictions using this “k” with the
experimental data. Submit your Matlab program(s) to the 10.37 course website.
N.B. Notice that in this type of “pseudo-first-order” experiment, one can determine “k” without knowing
[C2H3]o, the calibration constant “m” relating the signal to [C2H3], what the products of the reaction are, nor
what the competing reactions are (that contribute to r0). Because of these simplifications, this type of
experiment is very widely use’d to determine rate constants.
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Problem 2 Solution
d [C2 H 3 ]
a) − rC2 H 3 = − Eq 5
dt
Substitute Eq 3 into Eq 5
− rC2 H 3 = −
d [C 2 H 3 ]
=−
(
d [C 2 H 3 ]o e −t τ ) 1
= [C 2 H 3 ]o e −t τ Eq 6
dt dt τ
Substitute Eq 3 into Eq 2:
− rC2 H 3 = (k 0 + k [C 2 H 4 ])[C 2 H 3 ] = (k 0 + k [C 2 H 4 ])[C 2 H 3 ]o e − t τ Eq 7
Set Eq 6 = Eq 7 and simplify:
[C 2 H 3 ]o 1 e −t τ = (k 0 + k [C 2 H 4 ]o )[C 2 H 3 ]o e −t τ → τ= Eq 8
τ k 0 + k [C 2 H 4 ]o
algebraic relationship between τ and k
Substitute Eq 3 into Eq 1:
S (t ) = b + m[C 2 H 3 ](t ) = b + m[C 2 H 3 ]o e − t τ Eq 9
Substitute Eq 8 into Eq 9:
−t
S (t ) = b + m[C 2 H 3 ]o e −t τ
= b + m[C 2 H 3 ]o
Compare Eq 10 and Eq 4 to define:
e
0
1
k + k [C H ]
2 4 o
Eq 10
. I N
Bn = b An = m[C2 H 3 ]o
τn =
1
V
k 0 + k [C2 H 4 ]o,n
E
Only τn depends on k and [C2H4]o,n.
S S
.B
b) See the Matlab solution provided. To determine k, fit 1/τn vs. [C2H4]o,n to a straight
line. Slope = k (L/mol-s), y-intercept = k0 (1/s). Figures from Matlab are copied below.
k=1.11x107 L/mol-s
W
W
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. I N
V E
S S
.B
W
W
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Problem 1. The microorganism Mycobacterium vaccae is able to grow with ethane as the
sole source of carbon and energy and NH as the nitrogen source. The limiting substrate
3
is ethane, and Y =22.8 gram dry weight per mole of ethane. {Y = Yield of biomass (x)
sx sx
a. Except for small amounts of S and P, an analysis of dry cell mass is C, 47.60 wt%; N,
7.30 wt%; H, 7.33 wt%; ash, 3.00 wt%. The remainder is taken to be oxygen, which
can not be detected in the analysis. Determine the elemental composition for the ash-
free biomass, CH O N , and the formula weight per C-atom. Also determine Y , in
a b c
V E
b. Calculate the oxygen consumption Y (moles of O per C-mole of biomass) when it is
2 2 a b
xo
Sc S 2
assumed that CO , H O and CH O N are the only metabolic products. Write the full
.B
stoichiometric equation for the growth process, and determine the heat evolved per
kilogram dry weight. Assume ΔH
W
W
Problem 2. The gas phase homogeneous oxidation reaction
2 NO + O2 Æ 2 NO2
rNO = -2k[NO]2[O2]
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. I N
a. Consider a well-mixed batch reactor with initial enzyme concentration [E]0 and
V E
initial substrate concentration [S]0. Write expressions for the rate of change of
concentration of [S], [ES], [E], and [P] in terms of k1, k2, and Keq,1, and
concentration variables.
S S
.B
b. Write a Matlab function that solves this set of differential equations for the
concentration of all species in time given inputs k1, k2, Keq,1, [E]0, [S]0.
W
c. The pseudo-steady approximation may be applied on the reactive intermediate
W
species [ES]. This approximation is:
d[ES]
≈ 0 . Using this pseudo-steady
W dt
approximation, verify that the rate of change of [S] is given by the expression:
d[S] v [S]
= − max . What are v max and K M in terms of the other constants in this
dt K M + [S]
problem: k1, k2, Keq,1, [E]0, [S]0?
d[S]
d. What does the rate simplify to in the limit [S] >> K M ? What about the limit
dt
K M >> [S] ?
e. Consider the following conditions: k1=109 liter/mole-s, k2=1 s-1, Keq,1= 1
liter/mole, [E]0=10-6 M, [S]0=0.01 M. Find analytical solutions for [S](t), [ES](t),
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d[S]
and [P](t). Hint: determine what regime these conditions lie within.
dt
Compare the analytical solution with the full numerical solution by plotting them
together: plot [S](t), [ES](t) and [P](t) for both the numerical and analytical
solutions (three plots). Use a solid line for the analytical solutions and open
symbols for the numerical solutions. Run the simulation at least until the
conversion XP = [P]/[S]0 ≥ 99%. After approximately how much time does the
pseudo-steady approximation become valid? Hint: look at the short-time
behavior of [ES](t) in your numerical solution to find the answer.
. I N
V E
S S
.B
W
W
W
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Problem 1.
a.
C: H: O: N=47.60%/12: 7.33%/1: (1-47.60%-7.30%-7.33%-3.00%)/16: 7.30%/14=1: 1.85: 0.55:
0.13
Therefore, the elemental composition for the ash-free biomass is CH1.85O0.55N0.13.
Since ethane is the sole carbon source, from the conservation of C-atom, we know
Ysx=moles of biomass(x)/moles of ethane(s)
=
b.
. I N
2 2 a b c
V E
If assuming that CO , H O and CH O N are the only metabolic products, then the overall
metabolic reaction is
S S
0.5 C2H6+Yso O2+Ysn NH3 → Ysx CH1.85O0.55N0.13 + YscCO2 + Ysw H2O
.B
From a), we already got Ysx=0.451.
Use mass balance conditions on each atom:
C: 0.5*2=Ysx+Ysc
N: Ysn=Ysx*0.13
W
W
H: 0.5*6+Ysn*3=Ysx*1.85+Ysw*2
O: Yso*2=Ysx*0.55+Ysc*2+Ysw
W
After solving this set of linear equations, we finally get
Ysc=0.549 (mol CO2/C-mol ethane),
Ysn= 0.0589 (mol NH3/C-mol ethane),
Ysw=1.17 (mol H2O/C-mol ethane),
Yso=1.26 (mol O2/C-mol ethane)
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. I N
V E
S S
.B
W
W
W
Problem 2.
NO + O 2 ⎯⎯→
k1
NO3
NO3 ⎯⎯→
k -1
NO + O 2
NO3 + NO ⎯⎯→
k2
2NO 2
So the reaction rates: r1=k1[NO][O2], r-1=k-1[NO3], r2=k2[NO3][NO]
If using PSSH for the intermediate NO3, we have
d[NO3 ]
= k1[NO][O2 ] - k -1[NO3 ] - k 2 [NO3 ][NO] = 0
dt
k1[NO][O2 ]
. I N
From this we can obtain [NO3 ] =
k -1 + k 2 [NO]
V E
Thus
rNO =−
d[NO]
S S
= − k1[NO][O2 ] + k -1[NO3 ] - k 2 [NO3 ][NO]
.B
dt
k [NO][O2 ]
= −k1[NO][O2 ] + (k -1 - k 2 [NO]) 1
W
2k1k 2 [NO]2 [O 2 ]
k -1 + k 2 [NO]
=−
W k -1 + k 2 [NO]
W
In order to have third-order reaction kinetics as the form rNO = −k effective forward [NO] [O 2 ] , we
have to assume k-1>> k2[NO], so that the overall reaction rate for NO is
2
2k1k 2 [NO]2 [O 2 ]
rNO = −
k -1
2k1k 2
where k effective forward =
k -1
It is therefore under the condition when k-1~ k2[NO] or k-1<< k2[NO] for rNO to deviate
significantly from the normal third-order expression above.
Also let’s see what happens to the activation energy.
2k1k 2
E a, overall ∝ ln ∝ E a1 − E a, -1 + E a2 ~ΔH1, rxn+Ea2
k -1
If Ea1+Ea2-Ea, -1~ΔH1, rxn+Ea2<0, then we can have a negative apparent activation energy, for
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example, if elementary step 1 has a significantly negative ΔH1, rxn, so as long as Ea2 is not too high
the overall process will have a negative Ea, overall.
For the reverse reaction of the overall reaction, including the reverse reaction for the second
elementary step, i.e.
NO + O 2 ⎯⎯→
k1
NO3
NO3 ⎯⎯→
k -1
NO + O 2
NO3 + NO ⎯⎯→
k2
2NO 2
2NO 2 ⎯⎯→
k -2
NO3 + NO
and still using PSSH on the intermediate NO3
d[NO3 ]
= k1[NO][O2 ] - k -1[NO3 ] - k 2 [NO3 ][NO] + k - 2 [ NO 2 ]2 = 0
dt
we can have the intermediate concentration:
k1[NO][O2 ] + k -2 [ NO 2 ]2
. I N
[NO3 ] =
k -1 + k 2 [NO]
V E
Then in this case, the overall reaction rate is
rNO =−
d[NO]
S S
= −k1[NO][O2 ] + k -1[NO3 ] - k 2 [NO3 ][NO] + k - 2 [NO 2 ]2
.B
dt
k [NO][O2 ] + k - 2 [NO 2 ]2
= −k1[NO][O2 ] + (k -1 - k 2 [NO]) 1 + k - 2 [NO 2 ]2
W k -1 + k 2 [NO]
2(k -1k - 2 [NO 2 ]2 - k1k 2 [NO]2 [O 2 ])
=
W k -1 + k 2 [NO]
W
Again, if k2[NO]<<k-1, then
rNO = 2 k-2[NO2]2 – 2 k1k2/k-1 [NO]2[O2]
Notice that the second term is what we got before for the forward reaction, i.e.
kforward=2k1k2/k-1
The first term gives the effective rate constant for the reverse process:
kreverse=2k-2
Note that kforward/kreverse = k1k2/k-1k-2 = Kc1Kc2 = Kc,overall where Kc’s are equilibrium constants.
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Prob. 3
a. For the reactions
S + E ⎯⎯→
k1
E -S
E - S ⎯⎯→
k -1
S+ E
E - S ⎯⎯→
k2
P+E
We can write down
d[S]
= −k1[S][E] + k -1[E - S]
dt
d[E]
= − k1[S][E] + k -1[E - S] + k 2 [E - S]
dt
d[E - S]
= k1[S][E] − k -1[E - S] − k 2 [E - S]
dt
d[P]
= k 2 [E - S]
dt
. I N
With law of mass action on enzyme [E] + [E - S] = [E]0 , [S] + [P] + [E - S] = [S]0 , [P](t=0)=0,
V E
b.
function [t,conc] = odehw2_prob3(k1, k2, keq1, tmax)
S S
param = [k1,k2,keq1];
.B
W
%initial concentrations
%conc0 = ([S],[ES],[E],[P])
conc0 = [0.01,0,1e-6,0];
W
W
%use ode15s at the function derivhw2
%t is the time vector output
%conc is the 4 column matrix solution containing the concentrations of
%[S],[ES],[E],[P]
options = odeset('AbsTol', 1e-9, 'RelTol', 1e-6);
[t,conc] = ode15s(@derivhw2_prob3,[0;tmax],conc0,options,param);
%extract constants
k1 = param(1);
k2 = param(2);
keq1 = param(3);
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%concS = [S] in M
%concES = [ES] in M
%concE = [E] in M
%concP = [P] in M
. I N
%put derivative results back in column vector format for MATLAB
derivs = [dconcSdt; dconcESdt; dconcEdt; dconcPdt];
V E
return;
S S
.B
c. Using this pseudo-steady approximation on intermediate species ES,
d[E - S]
= k1[S][E] − k -1[E - S] − k 2 [E - S] =0
dt
we know
W
W [E - S] =
k1[S][E]
k -1 + k 2
W
Using mass balance condition [E] + [E - S] = [E]0
We know
[E]0
[E - S] =
k + k2
1 + -1
k1[S]
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d[S] V [S]
= − max ≈ −Vmax
dt [S] + K m
In the limit [S]<<Km, from
d[S] V [S]
= − max
dt Km
This gives an exponential function for [S](t)
. I N
[S](t) = [S](t = 0) exp(−
Vmax
Km
V
E
t) = [S]0 exp(− max t)
V Km
While for [ES],
S S
[ES](t) =
[E]0
k
1+ M
[E]
.B
[E] V
≈ 0 [S] = 0 [S]0 exp(− max t)
kM kM Km
W[S]
And for [P]
W
W
Vmax
[P](t)=[S]0-[ES](t)-[S](t) ≈ [S]0 [1 − exp(− t)]
Km
Use matlab to solve the following non-linear ODE IVP:
d[S] k
= −k1[S][E] + 1 ([E]0 - [E])
dt K eq, 1
d[E] k
= − k1[S][E] + ( 1 + k 2 )([E]0 - [E])
dt K eq, 1
d[P]
r= = k 2 [E - S] = k 2 ([E]0 - [E])
dt
with the initial conditions [S]t=0=[S]0=0.01M, k1=109 liter/mole-s, k2=1 s-1, Keq,1= 1 liter/mole, and
[E]0=10-6 M. From d[ES]/dt=0, we can determine the time to reach pseudo steady state is
approximately 7×10-9 sec, which is really really short. For this specific condition, pseudo steady
state works very well. This may also be seen from a direct comparison of the analytical/full
numerical solutions [ES](t) plots on a short time scale. [E-S] should rapidly rise from zero to the
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PSSA value (on the order of 10-8 seconds). The only observable difference between the
numerical and analytical solutions is this initial jump in [E-S] on the short time scale.
[S](t)[M]
0.01
numerical
0.009 analytical
0.008
0.007
0.006
[S][mol/L]
0.005
0.004
0.003
. I N
0.002
0.001
V E
0
0 0.5 1 1.5 2
S
2.5
S
3 3.5 4 4.5 5
.B
t[sec]
x 10
6
1
x 10
-8
W [ES] vs. t
0.9
W numerical
analytical
0.8
0.7
W
0.6
[ES] [M]
0.5
0.4
0.3
0.2
0.1
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
t[sec] 6
x 10
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[P](t)
0.01
0.009
0.008
numerical
0.007 analytical
0.006
[P][mol/L]
0.005
0.004
0.003
0.002
0.001
0
. I N
0 0.5 1 1.5 2 2.5
t[sec]
3
V
3.5
E
4 4.5
x 10
5
6
10
d[ES]/dt vs. t
S S
9
.B
8
W
7
W
d[ES]/dt [M/sec]
5 W
4
0
0 0.5 1 1.5 2 2.5 3
t[sec] -8
x 10
. I N
V E
S S
.B
W
W
W
10.37 HW 3
Spring 2007
Problem 1. A CSTR of volume 0.602 liters (constant density liquid phase) is operated in
which the following reaction occurs:
A+ B→C+ D
The feed rate of A is 1.16 liters/hr of a solution at concentration 5.87 mmol/L. The feed
Calculate the rate constant for this reaction assuming a mass-action rate law of the form:
r = k[ A][B] .
A+ B → B+C
. I N
with the second-order rate constant 1.15 x 10-3 m3/mol/ksec. The rate law is
r = k[ A][B] .
V E
S S
What volume of CSTR would be necessary to give 40% conversion of species A if the
feed concentration of A is 96.5 mol/m3, the feed concentration of B is 6.63 mol/m3, and
the flow rate is 0.5 m3/ksec?
.B
W
Problem 3. Two configurations of CSTRs are contemplated for performing reversible
hydrolysis of compound A to produce compounds B and C. The forward reaction is
W
pseudo-first-order with respect to A, with rate constant k1= 1.82 x 10-4 s-1. The reverse
reaction is second-order with rate constant k-1 = 4.49 x 10-4 M-1s-1 .
W
(1) A → B + C; r1 = k1[ A]
(2) B + C → A; r2 = k −1[B][C]
The feed is a dilute aqueous solution of A (concentration 0.25 mol/L) at a rate of 0.25
liters per hour.
b) three 5-liter CSTRs in series, with 75% of product species B & C selectively removed
between stages 1 and 2 and between stages 2 and 3, with appropriate adjustment in flow
rate; the volumetric flow rates in the two streams leaving a separator are proportional to
the total number of moles of A, B, and C in each stream. See the separator diagram
below.
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Separator
If q is the volumetric flow rate and F is the molar flow rate, then the separator follows the
relationships:
FA2 = 0
FB 2 = 0.75 FB0
FC 2 = 0.75FC 0
q1 F + FB1 + FC1
= A1
q2 FA2 + FB2 + FC 2
A full flow diagram is shown below.
. I N
V E
S S
.B
W
W
W
Determine the steady-state production of compound B in mol/h for options a) and b).
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10.37 HW 3
Spring 2007
Problem 1. A CSTR of volume 0.602 liters (constant density liquid phase) is operated in
which the following reaction occurs:
A+ B→C+ D
The feed rate of A is 1.16 liters/hr of a solution at concentration 5.87 mmol/L. The feed
Calculate the rate constant for this reaction assuming a mass-action rate law of the form:
r = k[ A][B] .
qA [A]0
qout [A] [B]
. I N
qB [B]0
V E
The only unknown quantities in the above figure are [B] and
qtot.
S S
.B
A volume balance on the carrier solvent gives the following
W
relationship (constant fluid density):
ξ& = rV [=]
mol
time
dn A
= FA0 − FA − ξ& = [ A]0 q A − [ A]qout − ξ& .
dt
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dnB
= FB0 − FB − ξ& = [B]0 q B − [B]qout − ξ& .
dt
[B]0 q B − ξ&
[B] = .
qout
ξ&
V E
k=
[ A][B]V
(4.23 mmol/h) S S
.B
L
k= = 0.357 = 357M −1h −1
(1.094 mmol/L)(18.0 mmol/L)(0.602 L ) h mmol
W
W
W
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A+ B → B+C
with the second-order rate constant 1.15 x 10-3 m3/mol/ksec. The rate law is
r = k[ A][B] .
What volume of CSTR would be necessary to give 40% conversion of species A if the
feed concentration of A is 96.5 mol/m3, the feed concentration of B is 6.63 mol/m3, and
the flow rate is 0.5 m3/ksec?
q [A]0 [B]0
[A] [B] [C]
. I N
Define the extent of reaction:
mol
V E
ξ& = rV[=]
time
S S
.B
Define the conversion in terms of the variables of the
problem:
q[ A]0
W
A material balance on species A gives the following
equation:
dn A
= FA0 − FA − ξ& = [A]0 q − [ A]q − ξ&
dt
At steady state:
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[ A]0 q − [ A]q [ A]
XA = =1−
q[ A]0 [ A]0
[ A] = (1 − X A )[ A]0
dnB
= FB0 − FB + 0ξ& = [B]0 q − [B]q
dt
At steady state:
[B] = [B]0 .
ξ& = rV = k[ A][B]V ,
. I N
the steady state A balance becomes:
V
0 = [ A]0 q − [ A]q − ξ& = ([ A]0 − [ A])q − k[ A][B]V .
E
S S
.B
Using the expressions derived for [B] and [A] in terms of
given values, we find:
W
0 = [ A]0 X A q − k[ A]0 (1 − X A )[B]0 V
W
Solving the equation for V we find:
V = W [ A]0 X A q
=
X Aq
k[ A]0 (1 − X A )[B]0 k (1 − X A )[B]0
(0.40)(0.5 m 3 /ksec)
= = 43.7 m 3
(1.15 ×10 m /(mol ⋅ ksec))(1 − 0.40)(6.63 mol/m )
V −3 3 3
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b) three 5-liter CSTRs in series, with 75% of product species B & C selectively removed
between stages 1 and 2 and between stages 2 and 3, with appropriate adjustment in flow
rate; the volumetric flow rates in the two streams leaving a separator are proportional to
the total number of moles of A, B, and C in each stream. See the separator diagram
below.
. I N
Separator
V E
S
q2 FA2 FB2 FC2
S
.B
relationships:
W
If q is the volumetric flow rate and F is the molar flow rate, then the separator follows the
FA 2 = 0
W FB 2 = 0.75FB 0
W q1
FC 2 = 0.75FC 0
= A1
F + FB1 + FC1
q2 FA2 + FB2 + FC 2
A full flow diagram is shown below.
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Determine the steady-state production of compound B in mol/h for options a) and b).
First, consider the 1-reactor case. Draw a diagram of the
situation (the control volume).
. I N
Define extents of reaction:
V E
ξ&1 = r1V = k1[ A]V
S S
.B
ξ&2 = r2V = k −1[ B][C ]V
W
Steady state A, B, and C material balances give the
following equations:
W
0 = FA0 − FA − ξ&1 + ξ&2
W
0 = F − F + ξ& − ξ&
B0 B 1 2
0 = FC 0 − FC + ξ&1 − ξ&2
Notice that:
FB0 = FC 0 = 0 .
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FB = FC
q0 [ B] = q0 [C ]
[ B] = [C ]
. I N
Dividing by q0 and solving for [A] we get:
W
single variable, [B] using our two new equations:
W
0 = FA0 − FA − ξ&1 + ξ&2
W
0 = q0 ([ A]0 − [ A]) − k1V [ A] + k −1V [ B][C ]
0 = q0 ([ A]0 − ([ A]0 + [ B]0 − [ B ])) − k1V ([ A]0 + [ B]0 − [ B]) + k −1V [ B][ B]
0 = a[ B ]2 + b[ B ] + c
a = (k −1V )
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b = (q0 + k1V )
− b ± b 2 − 4ac
[ B] =
2a
(b 2
− 4ac ) > 0 ,
[ B] =
− b + b 2 − 4ac
V E
2a
S S
.B
with no fear of getting a negative or imaginary result.
W
a = (k −1V ) = (4.49 ×10 M s )⎜
⎛ 3600s ⎞ L2
W −4
⎟(15 L ) = 24.246
-1 −1
⎝ h ⎠ mol ⋅ h
W
b = (q0 + k1V ) = (0.25 L/h ) + (1.82 ×10 −4 s −1 )⎜
⎛ 3600s ⎞
⎝ h ⎠
⎟(15 L ) = 10.078
L
h
c = 0 − (1.82 ×10 −4 s −1 )⎜
⎛ 3600s ⎞ mol
[B] = 0.172 M
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⎛ L⎞
FB = q0 [B] = ⎜ 0.25 ⎟(0.172 M ) = 0.0430 mol/h
⎝ h⎠
. I N
V E
S S
.B
W
W
W
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q0=0.25L/h
V=5 L
[A]0=0.25M
[A] [B] [C]
[B]0=[C]0=0M
S V
0 = a[B]2 + b[B] + c
.B S
0 = (k −1V )[B]2 + (q0 + k1V )[B] + (− q0 [B]0 − k1V[ A]0 − k1V[B]0 )
a = (k −1V ) W
b = (q0 + k1V ) W
W
c = (− q0 [B]0 − k1V[ A]0 − k1V[B]0 )
− b + b 2 − 4ac
[ B] =
2a
Plugging in the numbers, we find the quadratic coefficients
to be:
( )
⎛ 3600s ⎞
a = (k −1V ) = 4.49 ×10 −4 M -1s −1 ⎜ ⎟(5 L ) = 8.082
L2
⎝ h ⎠ mol ⋅ h
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c = 0 − (1.82 ×10 −4 s −1 )⎜
⎛ 3600s ⎞ mol
⎟(5 L )(0.25M ) − 0 = −0.819
⎝ h ⎠ h
Plugging the quadratic coefficients into the formula for
[B] we find:
[B] = 0.168 M
. I N
V E
S S
.B
W
W
W
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q1
q0=0.25 L/h
Separator [A]1
[A]0 = 0.082 M
1 [B]1
[B]0=[C]0=0.168 M
q2
[A]2
[B]2
FA 2 = 0
. I N
FB 2 = 0.75FB 0
FC 2 = 0.75FC 0
V E
q1 F + FB1 + FC1
= A1
q2 FA 2 + FB 2 + FC 2
S S
.B
Hence using the definition of molar flow rate, the
W
knowledge that [B]0 = [C]0, and the above separator
relationships, we find that:
q1 W
(q0 [ A]0 ) + 0.25(q0 [B]0 ) + 0.25(q0 [C]0 ) [ A]0 + 0.5[B]0
q2
q1
=
W 0 + 0.75(q0 [B]0 ) + 0.75(q0 [C]0 )
= = = 0.659
q2 1.5[B]0 1.5(0.168)
q1 = 0.659q2
0.25 L/h
q2 = = 0.151 L/h
1.659
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q0 0.25 mol
[ A]1 = [ A]0 = 0.082 = 0.205 mol/L .
q1 0.100 L
FB1 = 0.25FB 0
. I N
[B]1 = 0.25
q0
q1
[B]0 = 0.25
0.25
0.100
0.168
mol
L
E
= 0.105 mol/L
V
[ B ]1 = [C ]1
S S
.B
W
W
W
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(
a = (k −1V ) = 4.49 ×10 −4 M -1s −1 ⎜)
⎛ 3600s ⎞
⎟ (5 L ) = 8.082
L2
⎝ h ⎠ mol ⋅ h
V
c = −1.026
mol
h
S S
The quadratic solution gives:
.B
[B] = 0.204 M
W
W
Solving for [A] from the [A]/[B] relationship we find:
W
[ A] = ([ A]0 + [B]0 − [B])
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q1
q0=0.100 L/h
Separator [A]1
[A]0 = 0.106 M
2 [B]1
[B]0=[C]0=0.204 M
q2
[A]2
[B]2
q2 =
q0
=
0.100 L/h
= 0.0595 L/h
. I N
1.680 1.680
V E
q1 = q0 − q1 = (0.100 − 0.0595)
L
h
S S
= 0.0405 L/h
W
The concentrations of [A], [B], and [C] into the next
reactor are:
q
W
FA0 = q0 [ A]0 = FA1 = q1[ A]1
0.100 mol
[ A]1 = 0 [ A]0 = 0.106 = 0.262 mol/L .
q1 0.0405 L
FB1 = 0.25FB 0
q 0.100 mol
[B]1 = 0.25 0 [B]0 = 0.25 0.204 = 0.126 mol/L
q1 0.0405 L
[ B ]1 = [C ]1
Lastly, we rename our concentrations and proceed to reactor
3.
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( )
⎛ 3600s ⎞
a = (k −1V ) = 4.49 ×10 −4 M -1s −1 ⎜ ⎟(5 L ) = 8.082
L2
⎝ h ⎠ mol ⋅ h
(
b = (q0 + k1V ) = (0.0405 L/h ) + 1.82 ×10 −4 s −1 ⎜ )
⎛ 3600s ⎞
⎟(5 L ) = 3.3165
L
⎝ h ⎠ h
c = (− q0 [B]0 − k1V[ A]0 − k1V[B]0 )
⎛ L⎞
(
c = ⎜ − 0.100 ⎟(0.126M ) − 1.82 ×10 −4 s −1 ⎜
⎝ h⎠
)
⎛ 3600s ⎞
⎝ h ⎠ N
⎟(5 L )[0.262 + 0.126]M
. I
c = −1.284
mol
h
V E
The quadratic solution gives:
[B] = 0.243 M
S S
.B
Solving for [A] from the A/B relationship equation we find:
W
[ A] = ([ A]0 + [B]0 − [B])
W
[ A] = 0.262 M + 0.126 M − 0.243 M = 0.145 M
W
Since there is no separator, the amount of B recovered on
this step is just the amount leaving the reactor:
⎛ L⎞
FB3E = [B]q0 = (0.243M)⎜ 0.0405 ⎟ = 0.0098mol/h
⎝ h⎠
Thus the total amount of B recovered by this path is:
mol mol
FB = FB1E + FB 2 E + FB 3 E = (0.0315 + 0.0153 + 0.0098) = 0.0566
h h
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mol
FB ,3rctr = (0.0566 ± 0.0011)
h
mol
FB ,1rctr = (0.0430 ± 0.0009 )
h
V E
S S
.B
W
W
W
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Problem 1:
Biodiesel@MIT is working to convert the waste cooking oils from local dining halls and
restaurants into diesel fuel to run the MIT shuttle buses.
Waste cooking oils can be converted to biodiesel in several ways. One way is by gas-
phase pyrolysis:
This can be modeled as first-order irreversible reaction with a measured k=5x10-3 min-1 at
150 C and a measured Ea=85 kJ/mole.
Pure cooking oil is injected into a hot (T=227 C) reactor at a rate of 2.5 mole/min. At this
temperature all the species are in the vapor phase. The steady-state pressure in the reactor
is 10 atm.
conversion?
. N
(a) If the reactor is a CSTR, what reactor volume is required to achieve 90%
I
(b) If the reactor is a PFR and the pressure drop is negligible, what reactor volume is
required to achieve 90% conversion?
V E
(c) If you had a PFR half the volume you computed in part (b), and then fed its output
S S
into a CSTR half the volume you computed in part (a), what would the conversion
be? What if you hooked them up the other way round: the half-size CSTR first
.B
and the half-size PFR afterwards?
Suppose the reaction is carried out in a batch reactor, by filling it with enough
W
cooking oil and heating rapidly to 227 C, so that when the oil all vaporizes, but before
any significant reaction has occurred, the initial pressure in the reactor will be 2.7
atm.
W
W
(d) What will the pressure be in the isothermal batch reactor when the reaction has
run to 90% conversion?
(e) What would the batch reactor volume have to be if we were to process 3600
moles/day (= 2.5 moles/minute) of cooking oil this way? Assume that the batch
reactor can be emptied and refilled very rapidly, and that it is not necessary to
clean the reactor between batches.
(f) Which reactor (CSTR, PFR, batch) would you recommend be used for this
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Problem 2: Do Fogler problem 4-19 parts (a) through (e). This problem is about a
microreactor constructed by our new Department Head and some of his former graduate
students.
For part (c), does the pressure ratio profile for the new particle diameter make physical
sense? Why or why not? Decrease G (superficial mass velocity) to 3.5 kg/(m2*s) and re
plot the molar flow rates, X (conversion) and y (pressure ratio). Does the pressure ratio
make physical sense? Turn in plots for both cases (original G and new G).
Print out hard copies of all Matlab programs, and all figures, and staple them to your
handwritten solutions. Submit your Matlab programs to the 10.37 course website.
. I N
V E
S S
.B
W
W
W
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Problem Set 4
Given:
T0 = 150 C k(T0) = k0 = 5*10-3 (min-1) Ea = 85 kJ/mol
FA,0 = 2.5 mol/min yA,0 = 1 T = 227 C
X = 0.9 P = 10 atm
Next, make a stoichiometric table for the flow system (see Table 3-4 in Fogler). This
table applies to both a PFR and CSTR reactor.
Species
A
Feed Rate to Reactor
(mol/min)
FA0
Reactor (mol/min)
FA = FA0(1 – X)
B
C
0
0
FA0X
3FA0X
V E FB = FA0X
FC = 3FA0X
Total FA0
S S FT = FA0(1 + 3X)
.B
Since this is a gas-phase reaction, with a change in the total number of moles, the
W
volumetric flow rate (ν) will not be constant. Simplify Eq 3-41 in Fogler for the steady
state (constant P and T) ideal gas case to:
F
W F (1 + 3X )
ν = ν o T = ν 0 A0
F
T0 F
F RT
= ν 0 (1 + 3X ) = A0
P
(1 + 3X )
W
A0
a) CSTR
The design equation for CSTR volume in terms of conversion is (Eq 2-13 in Fogler):
VCSTR,a = = A0 = A0 = 0 =
(− rA )exit k [A] k FA kFA0 (1 − X ) Pk (1 − X )
ν
Plugging in numbers:
mol L ⋅ atm
2.5 .082 (500.15K )(1 + 3(0.9 ))0.9
min mol ⋅K
VCSTR,a = = 1655.36L ≈ 1.7 ⋅103 L
1
(10atm ) 0.206255 (1 − 0.9 )
min
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b) PFR
Neglect pressure drop, so ν equation is the same as above. The design equation for a PFR
in terms of conversion is (Eq 2-16 in Fogler):
FA0 RT (1+ 3X ) (1+ 3X )
X X X X X
dX dX dX F RT
VPFR,b = FA0 ∫0
− rA
= FA0 ∫
0
k [A]
=FA0
0 k
FA∫= FA0
0
PkF∫A0 (1 − X )
dX = A0
Pk ∫ (1 − X ) dX
0
ν
From integration by parts (or an integral table):
x2
(1 + mx ) dx = (1 + m )ln 1 − x1 + m(x − x )
∫
x1
(1 − x )
1 − x2
1 2
(1 + mx ) dx = (1 + m )ln 1 − mx
x
When x1 = 0, this simplifies to: ∫
0
(1 − x )
1 − x2
2
. I N
V E
S S
.B
W
W
W
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First: PFR then CSTR, where the volume of each is ½ the volume calculated in parts a
and b.
FA0 FA1, FB1, FC1
X1
PFR equation will be the same as derived in part b, but with V = ½ VPFR,b and X = X1:
1 F RT 1 VPFR,b Pk 1
VPFR,b = A0 (1+ 3)ln − 3 X 1 ⇒ − (1 + 3)ln + 3X 1 = 0
2 Pk 1− X 1 2FA0 RT 1− X 1
There are many methods that can be used to find the roots of the above equation (solver
function in Excel, fsolve in Matlab, etc). For example, using fsolve in Matlab:
function [Xpfr]=partc;
V E
return
S S
.B
function F = pfr_eqn(X)
k = 0.206255; %1/min
T = 227+273.15; %K
FA0 = 2.5; %mol/min
P = 10; %atm W
R = 0.082; %L*atm/mol/K
W
V_pfr_b = 323.63; %L, from part b calculation
W
F = V_pfr_b*P*k/(2*FA0*R*T)-(1+3)*log(1/(1-X))+3*X;
return
Can also solve for X1 by hand using an iterative method. For example, using the
Newton-Raphson Method:
f ( xn )
xn +1 = xn − where f’(xn) is the derivative of f, evaluated at x = xn.
f ' ( xn )
Keep iterating until xn+1 ≈ xn.
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Again, solve the above equation either by hand or with a program to find that X2 ≈ 0.95
Now: CSTR followed by PFR, where the volume of each is ½ the volume calculated in
parts a and b.
FA0
. I N
CSTR equation will be the same as derived in part a, but with V = ½ VCSTR,a and X = X1:
F RT (1 + 3X 1 )X 1
V
F RT (1 + 3X 1 )X 1
E
1
2
VCSTR,a = A0
Pk (1 − X 1 )
⇒
1
2
VCSTR,a − A0
S S
Pk (1 − X 1 )
=0
W
Rearrange, divide by ∆V and take the limit as ∆V approaches zero to get:
d [FA0 (1 − X )] − FA0dX
dFA
dV
W dF
= rA ⇒ dV = A =
rA rA
=
rA
= FA0
dX
− rA
Integrate with the limits V = 0 when X = XA1 and V = ½ VPFR,b when X = X2 to get:
X 2 X2 X2 X2 X2
1 dX dX dX FA0 RT (1 + 3X ) F RT (1 + 3X ) dX
2
VPFR,b = FA0 ∫
X1
− rA
= FA0 ∫
X1
k [A ]
=FA0 ∫
X1
F
k A
= FA0
X 1
∫
PkFA0 (1 − X )
dX = A0
Pk ∫
X1
(1 − X )
ν
From integration by parts (or an integral table):
x2
(1 + mx ) dx = (1 + m )ln 1 − x1 + m(x − x ) ⇒ 1 F RT 1 − X1
∫ VPFR,b = A0 (1 + 3)ln + 3( X 1 − X 2 )
x1
(1 − x ) 1 − x2
1 2
2 Pk 1 − X 2
FA0 RT 1− X 1 VPFR ,b
(1+ 3)ln + 3( X 1 − X 2 ) − =0
Pk 1− X 2 2
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Now, consider an isothermal batch reactor system with P0 = 2.7 atm. Make a
stoichiometric table for the batch system (see table 3-3 in Fogler)
B 0
NA0X NB = NA0X
C 0
3NA0X NC = 3NA0X
d) The volume of the batch reactor is fixed, so the change in moles as the reaction
proceeds will cause an increase in P. For an isothermal, constant volume batch reactor
(Eq 3-38 in Fogler, rearranged):
P = P0 (1 + 3X ) = 2.7atm (1 + 3(0.9 )) = 9.99atm
e) Want to process 2.5 mol/min of cooking oil in the batch reactor (assume that the down
time between batches is negligible).
N A0
treact
= 2.5
mol
min
⇒ N A0 = 2.5
mol
treact
min
. I N
N A0 RT
2.5
mol
t react RT
min
V E
Assuming ideal gas, V batch =
P0
=
S
P0
S
dX − rAV k [A]V
k AV
kN A0 (1 − X ).B
Find treact from design equation for a constant volume batch reactor (Eq 2-6 in Fogler):
N
dt
=
N A0
=
N A0
= V
N A0
=
WN A0
= k (1 − X )
∫
dX
t
∫ W ⇒ ln
1
⇒
1 1
0
W
(1 − X )
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Homework 6
“Investigators sift through the debris from blast in quest for the
spokesman said it appears… likely that the [fatal] blast was caused
In the process, a T=200oF aqueous solution, 83 wt% ammonium nitrate, is fed into a
CSTR. When the process is running normally at steady state, about 140 kg/hr of the
aqueous solution is injected, and the temperature in the reactor, TR, is 510oF. At this
temperature, the water evaporates rapidly, but the molten ammonium nitrate remains in
the CSTR, slowly decomposing by this reaction:
k(T=510oF) = 0.307/hour
. I N
∆Hrxn(T=510oF) = -740 kJ/kg of ammonium nitrate
V E
500oF.
S S
Note that it takes about 2.2 MJ to convert a kg of liquid water at 200oF to a kg of steam at
Also, FYI:
Cp(steam) = 2 kJ/kg-degree F .B
W
Cp(liquid NH4NO3) = 0.8 kJ/kg-degree F
W
Neglect non-ideal mixing effects and assume that NH4NO3 enters as a liquid. Assume
that ∆Hrxn is approximately constant in the reactor temperature ranges of the problem. A
W
diagram is shown below.
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gaseous products at TR
Pure liquid
ammonium
liquid feed, including water and
nitrate at TR
ammonium nitrate at 200oF
CSTR
(a) During normal steady-state operation, what mass (kg) of ammonium nitrate resides in
the reactor? Note that there is negligible hold-up of any gases within the reactor.
(b) How much cooling capacity (in kW) is required for this reactor when it is running in
I N
steady state? If this is provided by excess cooling water with an average temperature
.
Ta=100oF, what is the product of the heat transfer coefficient and the area, UA, in kW/Fo?
V E
During the investigation, it was hypothesized that the temperature increased, accelerating
the reaction. The rate constant of the decomposition reaction increases with temperature,
S
e.g. at T=560oF, k=2.91 hr -1. The reaction follows the Arrhenius T-dependence.
S
.B
(c) Using the stability criteria explained in the vicinity of Eq. 8-75, should the reactor
operate stably at 510oF? What is the critical temperature above which runaway reaction
could occur?
W
W
It is believed that pressure fluctuations were detected in the feed stream and it was shut
off by a plant operator about 4 minutes before the explosion occurred.
W
(d) Write and (using Matlab) solve a set of differential equations describing what
happened in the reactor after the feed was shut off. Plot the temperature in the reactor vs.
time. Do you predict an explosion?
(e) Was the operator wise to quickly shut off the feed of aqueous ammonium nitrate
solution when he feared something was going wrong in the reactor? Is there something
else he should have done to prevent the disaster?
(f) Propose a procedure for safely starting-up and shutting-down a process like this (a
qualitative description will suffice).
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HOMEWORK 6 KEY
“Investigators sift through the debris from blast in quest for the
spokesman said it appears… likely that the [fatal] blast was caused
In the process, a T=200oF aqueous solution, 83 wt% ammonium nitrate, is fed into a
CSTR. When the process is running normally at steady state, about 140 kg/hr of the
aqueous solution is injected, and the temperature in the reactor, TR, is 510oF. At this
temperature, the water evaporates rapidly, but the molten ammonium nitrate remains in
the CSTR, slowly decomposing by this reaction:
k(T=510oF) = 0.307/hour
. I N
500oF.
V E
Note that it takes about 2.2 MJ to convert a kg of liquid water at 200oF to a kg of steam at
Also, FYI:
S S
.B
Cp(steam) = 2 kJ/kg-degree F
Cp(liquid NH4NO3) = 0.8 kJ/kg-degree F
W
Neglect non-ideal mixing effects and assume that NH4NO3 enters as a liquid. Assume
that ∆Hrxn is approximately constant in the reactor temperature ranges of the problem. A
W
diagram is shown below.
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gaseous products at TR
Pure liquid
ammonium
liquid feed, including water and
nitrate at TR
ammonium nitrate at 200oF
CSTR
V E
Also, ideal mixing is assumed.
S S
.B
(a) During normal steady-state operation, what mass (kg) of ammonium nitrate resides in
W
the reactor? Note that there is negligible hold-up of any gases within the reactor.
W
Input state: liquid water and liquid ammonium nitrate are
fed at 200oF
W
Reaction State: temperature is TR, negligible gases are
present
A = ammonium nitrate
B = N2 O
C = H2 O
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V E
Water mass balance
dmC
S S
.B
= m& Cin − m& Cout + 2ξ&
MWC
dt
Apply steady state
0 = m& Cin − m& Cout + 2k m A W
MWC
W
Equivalent mole balance:
MW A
W
0 = FCin − FCout + 2ξ&
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(b) How much cooling capacity (in kW) is required for this reactor when it is running in
steady state? If this is provided by excess cooling water with an average temperature
Ta=100oF, what is the product of the heat transfer coefficient and the area, UA, in kW/Fo?
⎛ ⎞ ⎛ ⎞
d⎜ ∑ ĉ p ,i miT ⎟ d⎜ ∑ c p ,i N iT ⎟
dH
= ⎝ i ⎠= ⎝ i ⎠ = d (m A ĉ p , AT ) = d (N A c p , AT )
dt dt dt dt dt
d H
dt I N
= ∑ m& i,in Ĥ i − ∑ m& j,out Ĥ j + Q& −W& s = ∑ Fi,in H i − ∑ F j,out H j + Q& −W& s
.
E
i j i j
.B
W
0 = FA,in H A,in + FC ,in H C ,in − FC ,out H C ,out − FB,out H B,out + Q&
W
Add and subtract the terms ± FA,in H A,out ± FC ,in H C ,out . We need to do
W
this to get enthalpy differences that we know into the
enthalpy balance, as absolute enthalpies have little
meaning.
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∆H rxn (TR ) = ∑ν
products
i H i (TR ) − ∑ν
reactants
i H i (TR ) = H B (TR ) + 2H C (TR ) − H A (TR )
( ) ( ) (
0 = m& A,in Ĥ A,in − Ĥ A,out + m& C ,in Ĥ C ,in − Ĥ C ,out − k(TR ) m A ∆Ĥ rxn (TR ) + Q& )
Now we need to know how to calculate the enthalpy
differences in the inflow streams: we need to heat up the
inflow to the reaction temperature, TR.
V E
S
o
H C ,in = molar enthalpy of liquid water at 200 F
H C ,out = molar enthalpy of steam at TR
(Ĥ C ,in ) (
S
.B ) (
− Ĥ C ,out = Ĥ (water,200°F ) − Ĥ (steam,500°F ) + Ĥ (steam,(500°F )) − Ĥ (steam,TR ) )
(Ĥ − Hˆ C ,out ) = (− 2.2MJ/kg ) − (T W ⎛ kJ ⎞⎛ 1MJ ⎞ ⎛
− 500° F )⎜⎜ 2 ⎟⎜
⎟ ⎟ = ⎜ −1.2 −
TR ⎞
⎟MJ/kg
W
C ,in R
⎝ kgF° ⎠
⎝ 1000kJ ⎠ ⎝ 500F° ⎠
(0.8TR −160°F )
(Ĥ ) ⎛ 0.8kJ ⎞
A,in − Ĥ A,out
W = −(TR − 200°F )⎜⎜
⎝ kgF° ⎠
( ) ( )
0 = m& A,in Ĥ A,in − Ĥ A,out + m& C ,in Ĥ C ,in − Ĥ C ,out − (k(TR ) m A ∆H rxn (TR ) ) + Q&
( ) ( )
Q& = −m& A,in Ĥ A,in − Ĥ A,out − m& C ,in Ĥ C ,in − Ĥ C ,out + (k(TR ) m A ∆H rxn (TR ) )
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⎛ (0.8(510°F ) −160°F ) ⎞
Q& = −(0.83)(140kg/h )⎜ − MJ/kg ⎟ + L
⎝ 1000 ⎠
⎛ (510°F ) ⎞
− (0.17 )(140kg/h )⎜ −1.2 − ⎟MJ/kg + ...
⎝ 500F° ⎠
Q& = UA(Ta − TR )
− 4.4MJ / h
Q& / (Ta − TR ) = UA = = 0.01073MJ / hF° = 0.00298kW / °F
(100 − 510)F°
. N
During the investigation, it was hypothesized that the temperature increased, accelerating
I
the reaction. The rate constant of the decomposition reaction increases with temperature,
e.g. at T=560oF, k=2.91 hr -1. The reaction follows the Arrhenius T-dependence.
V
Given two T values and two k values, calculate k(T). Note E
S S
that in an Arrhenius expression, an ABSOLUTE temperature
scale must be used. Recall the temperature in Rankine (an
.B
absolute scale) is just the Fahrenheit temperature plus
459.67.
k(T / °F ) = Aexp ⎜
⎛
W
− b
⎝ T / °F + 459.67 ⎠
⎞
⎟
k(510) = Aexp ⎜
⎛ W − b ⎞
⎟
k(560) = Aexp ⎜
W⎝ 510 + 459.67 ⎠
⎛ − b
⎝ 560 + 459.67 ⎠
⎞
⎟
⎛ k(510) ⎞
⎟ = − ln⎛⎜
0.307 ⎞ ⎛ b ⎞ ⎛ b ⎞
− ln⎜⎜ ⎟ ⎟=⎜ ⎟−⎜ ⎟
⎝ k(560) ⎠ ⎝ 2.91 ⎠ ⎝ 510 + 459.67 ⎠ ⎝ 560 + 459.67 ⎠
2.24906 = (5.0692E − 05)b
b = 44367
⎛ − 44367 ⎞
A = k(510) / exp⎜ ⎟ = 2.28E19h −1
⎝ 510 + 459.67 ⎠
Note that k(T) is very sensitive to small changes in the
activation energy (or b in this case).
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Ea
b= (°Rankine)
R
(c) Using the stability criteria explained in the vicinity of Eq. 8-75, should the reactor
operate stably at 510oF? What is the critical temperature above which runaway reaction
could occur?
G(T ) = R(T ) at steady state: R(T) is all the rest of the terms
. I N
in the enthalpy balance (multiplied by -1, divided by the
mass flow rate in)
( ) ( )
V E
− m& A,in Ĥ A,in − Ĥ A,out − m& C ,in Ĥ C ,in − Ĥ C ,out − Q&
R(T ) =
S
m& A,in S
.B
Near a steady state, there is no accumulation of A in the
reactor and:
m& A,in = km A
Thus G(T) simplifies to:
W
G(T ) = −∆Ĥ rxn
W
Since there is no outflow, the conversion must always be
W
unity. This makes the G(T) curve much simpler than it is
in the standard CSTR in Fogler.
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R(T)
G(T), R(T)
G(T)
510oF
Since both G(T) and R(T) are lines, there is only one
possible intersection and one possible steady state. If
. I N
you perturb the steady state to a slightly hotter
temperature, R>G and the system will cool down. If you
perturb the system to a slightly cooler temperature, G>R
V E
and the system will warm up. Thus the steady state is
STABLE.
S S
.B
Stability analysis is only useful for small perturbations
from a steady state. Determining the magnitude of a
W
perturbation that will cause the system to “blow up” is
W
beyond the scope of the problem.
W
The analysis in Fogler is to find perturbations that cause
motion from one low-temperature steady state to a higher
temperature steady state (ignition). As this transition is
not possible given our G and R curves, the analysis
required is much simpler.
It is believed that pressure fluctuations were detected in the feed stream and it was shut
off by a plant operator about 4 minutes before the explosion occurred.
(d) Write and (using Matlab) solve a set of differential equations describing what
happened in the reactor after the feed was shut off. Plot the temperature in the reactor vs.
time. Do you predict an explosion?
Unsteady Problem
m A (t = 0) = 378.5kg
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T (t = 0) = 510°F
Enthalpy:
d H d (N A H A + N B H B + N C H C ) d (N A H A ) dN A dH A
= = = HA + NA
dt dt dt dt dt
dH &
dt
dN A
= Q − FB ,out H B − FC ,out H C
HA +
dH A
N A = Q& − FB ,out H B − FC ,out H C . I N
dt dt
V E
Batch Reactor mole balances
dN A
= −kN A
S S
.B
dt
dN B
= 0 = −FB ,out + kN A
dt
FB ,out = kN A W
dN C
W
= 0 = −FC ,out + 2kN A
dt
W
FC ,out = 2kN A
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. I N
V E
S S
.B
W
W
W
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Code:
function [m,T]=hw6p1(tminutes);
%[m,T]=hw6p1(5); %run simulation for 5 minutes, crashes at ~4.5 minutes
thours = tminutes/60;
x0 = [378.5;510];
options = odeset('RelTol',10^-6,'AbsTol',10^-9);
[t,x] = ode15s(@odefun,[0,thours],x0,options);
m = x(:,1);
T = x(:,2);
figure(1);
plot(t*60,m);
title('NH_4NO_3 holdup');
ylabel('m')
figure(2);
plot(t*60,T);
title('Temperature in Reactor');
ylabel('T/degF')
return;
T = x(2); %degF
k = 2.28e19 *exp(-44367/(T+459.67));
. I N
Ta = 100; %degF
V E
dmdt = -k*m;
S S
%dTdt = (-k*dHrxn/cpa) + (UA*(Ta-T)/(m*cpa)) + (T*k); %slightly wrong
.B
dTdt = (-k*dHrxn/cpa) + (UA*(Ta-T)/(m*cpa)); %correct
derivs = [dmdt;dTdt];
return;
W
W
W
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Temperature Plot:
. I N
V E
S S
.B
Perturbing the most sensitive problem parameter, the
activation energy term, b, by +1% gives similar looking
plots with explosion times shifted to 3-8 minutes.
W
W
(e) Was the operator wise to quickly shut off the feed of aqueous ammonium nitrate
solution when he feared something was going wrong in the reactor? Is there something
W
else he should have done to prevent the disaster?
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. I N
Green circles represent initial conditions, red circles
represent final conditions after 4 hours of integration.
Black lines represent trajectories and connect green
V E
S S
circles to red ones. Diverging trajectories lead to a
temperature “explosion”. The absolutely final steady state
.B
would be an empty reactor at the temperature of the cooling
water.
W
It is clear that above ~425oF it is not safe to shut off the
W
reactor; this threshold “safety limit” temperature
increases slightly as mass holdup decreases. Since the
W
initial conditions are above this threshold, the sudden
shutoff of the feed was a BAD IDEA.
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function stabilitydiagram(tminutes);
thours = tminutes/60;
options = odeset('RelTol',10^-6,'AbsTol',10^-9);
mlist = linspace(200,500,21);
Tlist = linspace(350,560,21);
for(i = 1:length(mlist))
for(j=1:length(Tlist))
[t,x] = ode15s(@odefun,[0,thours],[mlist(i),Tlist(j)],options);
m = x(:,1);
T = x(:,2);
plot(m(end),T(end),'or'); %red stop
plot(m(1),T(1),'og'); %green go
plot(m,T,'-k'); %black trajectory
end
end
title('stability diagram at flow shutoff')
xlim([0,500])
ylim([0,600])
grid on;
hold off;
. I N
return
V E
T = x(2); %degF
k = 2.28e19 *exp(-44367/(T+459.67));
S S
.B
UA = 0.01073; %MJ/(h degF)
Ta = 100; %degF
W
dHrxn = -0.740; %MJ/kg NH4NO3
dmdt = -k*m;
W
dTdt = (-k*dHrxn/cpa) + (UA*(Ta-T)/(m*cpa)); %correct
derivs = [dmdt;dTdt];
return;
W
(f) Propose a procedure for safely starting-up and shutting-down a process like this (a
qualitative description will suffice).
Examples of ideas:
The flowrate could be turned on/shut off gradually
The concentration of ammonium nitrate could be ramped
up/down gradually
Greater cooling/heating control could be utilized at
startup and shutdown
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Problem 1.
A protein P reversibly binds a ligand L to f m l a complex C.The table below lists complex
concentration measured as a function of time t with varying initial ligancl concentrations ( [L],
= 1. 5 . or 15 pM). The initial protein concentration [PI, was always 1 nM. Estimate k,,, kd,
and Kd of the reaction. (Conaributed by 19 Bmmford).
. I N
Problem 2.
V E
S S
The objective of this exercise is to compare the volumetric productivity of a steady-state
.B
chenlostat to that of a batch reactor. The batch operating time is the time for exponential
biomass growth from X, to X plus a turnaround time F~,,,,.Show that the ratio of volumetric
+
X
frmnxttum.
biomass productivity for a chemostat vs. a batch reactor i s approximately !n ?i;
W
Problem 3.
W
W
The notion of computers with circuits built from cells has been proposed previously. If
the switches in such a computer involve changes in the level of expressed proteins, what
expression would describe the time to change from an "off state" (no expression) to an
"on state" (95% of the new steady-state level)? What would the half-time for switching
be in the following two cases: a) cells rapidly growing (doubling time 30 minutes) and a
stable protein (degradation half-tune one day); or b) cell not growing at all (infinite
doubling time) and a protein with a degradation half-time of 1 hour? How do these
switchmg times compare to those for silicon logic circuits? Would you invest in a
company developing such cellular computers?
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Problem 1.
The binding of protein P with ligand L to form complex C is reversible, as told
P + L ⎯⎯→
k on
C and C ⎯k⎯
off
→P + L
We are given a table with various initial concentrations of L in order to estimate kon and koff and
also Kd for the reaction.
dCC
= k on C P C L − k off CC
dt
Also from material balances and stoichiometry, we have CP+CC=CP0 and CL+CC=CL0, therefore
dCC
= k on (C P0 - C C )(CL0 − CC ) − k off CC
dt
In this problem, we can safely assume that CL0-CC≈CL0 since CL0>> CP0 in all three cases of
different CL0.
Thus, the integrated analytic expression for CC becomes
k on C P0 C L0 C C
CC = {1 - exp[-(k on C L0 + k off )t]} = P0 L0 {1 − exp[-(k on C L0 + k off )t]}
k on C L0 + k off C L0 + K d
k off
. I N
where K d ≡
k on
V E
y=a[1-exp(-bt)], where b is konCL0+koff, and a is
S
Therefore, if we plot CC w.r.t time for each cases of CL0, we can fit according to an exponential
S C P0 C L0
. Values for a and b are shown in the
following table. .B C L0 + K d
WL0(uM) a b
W 1
5
0.903
1.0436
1.1113
4.7047
W 15 0.9932 15.1079
One important observation in this table is that parameter a does not change much when initial
ligand concentration is changed, indicating CL0=1μM is already above the saturating value.
Therefore, value for koff can not be obtained accurately from this design of experiments. We can
only conclusively obtain the value for kon.
So we fit a linear express of b vs. CL0 to get kon.
kon=0.0010 nM-1 sec-1
An estimate on koff would be
0<=koff<<konCL0,min =0.0010 nM-1 sec-1*1uM=1 sec-1
Similarly an estimate on Kd is
0<= Kd<< CL0,min=1μM.
CL0=1uM
0.4
0.35
0.3
Concentration of C(nM)
0.25
0.2
0.15
0.1
0.05
0
. I N
0 0.05 0.1 0.15 0.2 0.25
time(t)
0.3
V
0.35
E
0.4 0.45 0.5
S
CL0=5uM
S
0.9
.B
0.8
W
0.7
W
Concentration of C(nM)
0.6
0.5 W
0.4
0.3
0.2
0.1
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
time(t)
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CL0=15uM
1
0.9
0.8
0.7
Concentration of C(nM)
0.6
0.5
0.4
0.3
0.2
0.1
0
. I N
0 0.05 0.1 0.15 0.2 0.25
time(t)
0.3
V
0.35
E
0.4 0.45 0.5
S S
.B
16
14
W
W
12
W
10
8
b
-2
0 5 10 15
CL0(uM)
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Problem 2.
For a steady state chemostat, the material balance on cell mass yields
F
D≡ =μ
V
the volumetric productivity is
F(X- X0)=μV(X- X0)
For a batch reactor, the material balance on cell mass yields
dX
= μX
dt
where the initial condition is X(t=0)=X0.
V
X0 E
+ μt turn
1
ln
X
+t
μ X 0 turn
S S
.B
In practice, for chemostat, in order to maximize the productivity of biomass (DX), the operating
condition for μ is close μmax. Therefore the ratio above is approximately
W X
+ μ max t turn
W ln
X0
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Problem 3.
The expression that would be suitable to describe the change of protein expression is:
k Pk r
CP = {1 − exp[−(γ P + μ )t ]}
γ r (γ P + μ )
where the meaning of each symbol is in accord with what we did in class.
The time required to change from an “off state” to an “on state” (95% of the steady-state value) is
ln 0.05
0.95 = 1 − exp[−(γ P + μ )t ] or t = −
γP + μ
a) if cells are rapidly growing with a doubling time 30 min and stable protein with a degradation
half-time one day, i.e.
ln2 ln2
= 30min and = 1 day
μ γP
So the half-time for switching is the time need to reach
0.95 ×
1
2
= 1 − exp[−(γ P + μ )t ]
. I N
t switching =
(γ P + μ )
1
- ln(1 - 0.95 × ) - ln(1 - 0.95 × )
2 =
ln 2
V
ln 2
1
E
2 ≈ 27.9 min
S
+
S
30 min 1day
.B
b) if cells are not growing at all and the protein with a degradation half-time one hour, i.e.
ln2
= 1 hr
W γP
W
So the half-time for switching is
1 1
- ln(1 - 0.95 × ) - ln(1 - 0.95 × )
W t switching =
(γ P + μ )
2 =
ln
1hr
2
+0
2 = 0.93hr
So in both cases, the switching times are much much longer than that of the current electronic
circuits, which is on the order of ~ns-μs. Thus, it would not be promising in realizing a computer
for practical uses.
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10.37 Spring 2007 Problem Set 10 Due Wednesday, May 9
Figure 1.
1) The catalytic reaction (A Æ B) takes place within a fixed bed containing spherical
porous catalyst X22. Figure 1 shows the overall rates of reaction at a point in the
reactor as a function of temperature for various entering total molar flow rates,
FT0.
a) Is the reaction limited by external diffusion?
. I N
b) If your answer to part (a) was “yes,” under what conditions [of those
V E
shown (i.e. T, FT0)] is the reaction limited by external diffusion?
d) If your answer to part (c) was “yes,” under what conditions [of those
S S
shown (i.e. T, FT0)] is the reaction limited by the rate of the surf
e) Is the reaction limited by internal diffusion?
.B
f) If your answer to part (e) was “yes,” under what conditions [of those
shown (i.e. T, FT0)] is the reaction limited by the rate of internal diffusion?
g) For a flow rate of 10 mol/hr, determine (if possible) the overall
W
effectiveness factor, Ω, at 360 K.
h) Estimate (if possible) the internal effectiveness factor, η, at 367 K.
W
i) If the concentration at the external catalyst surface is 1 mol/L, calculate (if
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10.37 Spring 2007 Problem Set 10 Due Wednesday, May 9
2) A large fraction of all the platinum-group metals that have ever been mined
currently reside in catalytic converters on automobiles. As noble metals prices rise
(prices remain near record high levels) and the number of vehicles in the world
increases, it is imperative to minimize the amount of catalyst employed, while still
meeting the emissions regulations. Your object in this problem is to first build a
Matlab simulation of a catalytic converter, and then explore the geometrical
tradeoffs involved that affect the total amount of catalyst employed.
The input to the converter is the car exhaust stream; when it is running fuel-rich (e.g.
during acceleration) it is 1200 moles/hr of N2, 200 moles/hr of CO2, 200 moles/hr of
H2O(steam), 20 moles/hr CO, and 4 moles/hr NO all at T=700 K and a total pressure
of 1 atm. The most difficult requirement is that output needs to be < 0.4 moles/hr of
NO. Assume that the rate-limiting (and essentially irreversible) elementary step is
. I N
Where M is a noble metal site and the fraction of the surface covered by CO--M and
NO--M is given by Langmuir-Hinshelwood equilibria:
V E
CO + M = CO—M
NO + M = NO—M
S S
Keq1 at 700 K= 1 (atm)-1
Keq2 at 700 K= 3 (atm)-1
.B
The N—M formed in the rate-controlling step rapidly combine to make and release
N2.
W
For the purposes of this problem you can neglect the binding by the other gas-phase
W
species at this temperature. (In the real system there are several other
complications…). To make the numerical solution easier, we suggest that you assume
W
that the partial pressure of CO is constant inside any pore, i.e.
[CO(inside pore)]=[CO,s]
and that you also assume that Keq2*PNO is negligible compared to Keq1*PCO. This
is approximately correct even if the chemistry is fast because the CO is present in
excess, and in any case Keq2*PNO is always << 1. If you are a careful engineer, you
can check the validity of these approximations after you have a solution in hand.
The converters are monolithic reactors, you can approximate the geometry as a lot of
8 mm i.d. pipes in parallel, with each pipe’s walls lined with a thin layer of porous
material (0.1 m2 platinum/ ml porous material).
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10.37 Spring 2007 Problem Set 10 Due Wednesday, May 9
a) Rewrite the rate law so it is first order with respect to the NO concentration in the
gas within the catalyst pores. It should have the form:
Rate= k’ RT * [NO]
. I N
b) Derive the Thiele modulus assuming the thin porous layer can be modeled as a
effectiveness factor?
V E
slab. Derive the concentration profile of the NO inside the pore. What is the
S S
c) Use a flux balance to find the overall effectiveness factor, omega, for the reaction.
.B
d) Using your overall effectiveness factor, which allows you to write the reaction
rate using the bulk NO and CO concentrations in the pipe, run a simulation for
W
this base case: the porous layer is 1 µm thick, the pipes are 20 cm long, and there
are 2000 identical pipes in parallel. Does this achieve the emission target for NO?
W
e) Compute how the NO conversion varies if you double the thickness of the porous
W
layer.
f) Compute how the NO conversion varies if you double the number of parallel
pipes.
g) Compute how the NO conversion varies if you double the length of the pipes.
h) Make a guess at a design that would achieve the same or better NO conversion as
the base case but uses less noble metal. Run a simulation for this case to see if
your estimate is right. Would the pressure drop be a lot different in your design
than in the base case? (You do not need to simulate the pressure drop.)
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b) Table 12-1 shows that external diffusion-limited ra varies with U1/2 and nearly linearly with
T. This is the case for:
FT0 = 10 mol/hr, all T
FT0 = 100 mol/hr, about 362K < T < 375K
W hr
W
actual_rate(internal_lim )
− rA' 5000
mol
hr
,367K
h) η =
W
ideal_rate(rxn_lim )
=
− rA' 5000
mol
hr
,367K
Extrapolate the reaction-rate limited portion of the FT0 = 5000 mol/hr curve up to 367 K.
1.2
η≈ = 0.8
1.5
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CA 1 sinh (φ1λ )
Ψ= = with λ = r / R = 1 / 2
C A,S λ sinh φ1
j) For a given FT0, the reaction rate will increase either exponentially or linearly with T (meaning
the needed pipe length to achieve a certain conversion will decrease either exponentially or
linearly with T).
external
ex ternal diffusion limited
L Rxn
limited
int
inteernal
rnal diffusion limited
T
. I N
V E
For a given T, increasing the flowrate will increase the pipe length needed for a given
S S
conversion. However, while in the external diffusion limited region, an increase in FT0 also
increases the reaction rate (i.e. decreases the pipe length). The higher rA will offset somewhat
the effect of the higher flow rate, and therefore the needed pipe length will increase slowly with
.B
FT0 while in the external-diffusion limited region. When the process is internal-diffusion or rxn
rate limited, rA no longer increases with FT0, so the pipe length needed for a given conversion
will increase sharply.
W
W
L W no external
limitations
external
diffusion limited
FT0
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2. a)
rlim = kθ NO − M θ CO − M
Volume of porous material
where θ i−M =
[i − M ]
[M ]o
Use the adsorption steps (rapid equilibrium) to find θ i−M .
K eq,2 = ⇒ θ NO−M =
PNO [M ] PNO [M ] [M ]o
Use and overall site balance to find [M] (concentration of empty sites).
. I N
[M ]o = [M ] + [CO − M ] + [NO − M ] = [M ] + θ CO−M [M ]o + θ NO−M [M ]o
V E
Substitute in the equations for θ i−M :
K eq,1 PCO [M ] S
K eq,2 PNO [M ]
S
[M ]o = [M ] +
[M ]o
[M ]o +
[M ]o .B [M ]o
W
Solve for [M] and use the simplifications given in the problem statement (Keq2PNO << Keq1PCO
and PCO = PCO,S):
W
[M ] = W
[M ]o
1+ K eq,1 PCO + K eq,2 PNO
=
[M ]o
1+ K eq,1PCO,S
− rNO = rlim
K P K P
= k eq,1 CO,S eq,2 NO
[M ]o
Area of noble metal
[M ]o [M ]o 1 + K eq,1 PCO,S
Volume of porous material
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b) We now have a rate expression that is first order in [NO]. The thickness of the catalyst on the
surface is small, so the curvature can be ignored and the catalyst is modeled as a slab:
Bulk gases
gases
[NO]S
x=L
x catalyst
pipe wall
. I N
At steady state, diffusion of NO inside the catalyst is governed by:
∂ 2 [NO ]
V E
D pores
∂x 2
+ rNO = 0
S S
D pores
∂ 2 [NO ]
∂x 2
− k "[ NO ] = 0
.B
W
Non-dimensionalize:
W
ψ ≡
[NO]
[NO]S W
λ≡
x
L
⇒
∂ 2 Ψ k" L2
−
∂λ2 D pores
Ψ=0
k" L2
φ2 ≡
D pores
∂2Ψ
The equation: − φ 2Ψ = 0
∂λ 2
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∂Ψ
2. = 0 (no flux at pipe wall)
∂λ λ =0
∂ψ
= − Aφe −λφ + Bφe λφ
∂λ
1
1 = Ae −φ + Aeφ ⇒ A=
e + eφ
N
−φ
.
Solution of the concentration profile of NO inside the catalyst (treated as a slab):
E I
ψ =
e − λφ + e λφ
e −φ + eφ
S V
.B S
We want the internal effectiveness factor (η) as a function of the thiele modulus (φ).
W
The actual reaction rate is the integral of the concentration times the first order rate constant over
W
the entire slab thickness. However, an easier way to find this is to use the fact that the flux at the
surface of the catalyst has to be equal to the total reaction occurring inside.
∂[ NO ] [ NO ]S ∂Ψ
actual rxn rate = (flux )(surface area ) = D pores Asurface = D pores Asurface
∂x L ∂λ λ =1
[ NO ]S − φe −φ + φeφ
actual rxn rate = D pores −φ φ
Asurface
L e +e
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D pores
[NO ]S − φe −φ + φeφ A
L e −φ + eφ surface
D pores − φe −φ + φeφ 1 eφ − e −φ
η= = = φ
k"[NO]S Vcatalyst k" L2 e −φ + eφ φ e +e
−φ
(note that the surface area exposed to the bulk gas divided by the volume of porous material is
equal to 1/L)
At steady state:
V E
[NO]S =
k c Asurface [NO]bulk
ηk"Vcatalyst + k c Asurface
=
k c [NO]bulk
S
ηk" L + k c
S
Substitute into the omega equation: .B
ηk c [NO]bulk ηk c W
Ω= =
W
[NO]bulk (ηk" L + k c ) ηk" L + k c
W
where kc = Dbulk/delta
dX NO − rNO AcV porous _ material Ωk"[NO]AcV porous _ material Ωk"[NO]0 (1 − X NO )AcV porous _ material
= = =
Note that the change in the number of moles can be ignored because epsilon ≈ 0 (mole fraction
of NO in the feed is extremely small).
The Vporous_material/Vreactor term is needed because the rate expression derived in part a) is per
volume of porous material, but the rate expression in the PFR design equation needs to be on a
per volume of reactor basis.
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In order to calculate kc, need to first calculate delta using the equation given in the problem
statement:
To calculate the superficial velocity (U) in each pipe, use the equation:
qo FNO ,o
U= =
Ac [NO]o Ac
The feed molar flow rate of NO in each pipe is found by dividing the total feed molar flow rate
of NO by the number of pipes:
FNO ,o ,total
FNO ,o =
N pipes
. I N
The concentration of NO in the feed is found by multiplying the feed mole fraction by the total
concentration:
V E
[NO]o = y NO ,o Ctot =
FNO ,o P
∑ Fi ,o RT
S S
.B
i
W
function [X1f,X2f,X3f,X4f,X5f] = HW10_P2_allparts();
%[X] = HW10_P2_allparts()
W
[z1,X1]
[z2,X2]
[z3,X3]
[z4,X4]
[z5,X5]
=
=
=
=
=
W
reactorsimulation(1E-6, 2000, 0.2);
reactorsimulation(2E-6, 2000, 0.2);
reactorsimulation(1E-6, 4000, 0.2);
reactorsimulation(1E-6, 2000, 0.4);
reactorsimulation(.4E-6, 5000, 0.2);
X1f = X1(length(z1));
X2f = X2(length(z2));
X3f = X3(length(z3));
X4f = X4(length(z4));
X5f = X5(length(z5));
figure(1);
plot(z1,X1);
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ylabel('NO conversion')
figure(2);
plot(z2,X2);
ylabel('NO conversion')
figure(3);
plot(z3,X3);
ylabel('NO conversion')
figure(4);
plot(z4,X4);
ylabel('NO conversion')
figure(5);
plot(z5,X5);
. I N
ylabel('NO conversion')
E
title('Thinner Catalyst Layer, More Pipes (same amount of noble metal)(part
h)')
V
return;
S S
.B
function [z,X] = reactorsimulation(thicknessofcatalyst,numberofpipes,...
lengthofpipes);
%a = NO
%b = CO
W
W
%Reactor/Catalyst Geometry and Chemistry
param.L = thicknessofcatalyst; %m
W
N = numberofpipes;
Lp = lengthofpipes; %m
%Reactor/Feed Conditions
param.Fa0 = ya0*Ftot; %NO feed molar flow rate into each pipe, in mol/s
Fb0 = yb0*Ftot; %CO feed molar flow rate into each pipe, in mol/s
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odeoptions = odeset('AbsTol',1e-9,'RelTol',1e-12);
[z,X]=ode15s(@diffeqs,[0 Lp],0,odeoptions,param);
return
T = param.T;
R = param.R;
kc = param.kc;
Ac = param.Ac;
. I N
L = param.L;
theta_b = param.theta_b;
Vporous_mat = param.Vporous_mat;
V E
Vreactor = param.Vreactor;
Ca0 = param.Ca0;
Fa0 = param.Fa0;
S S
Dpores = 1E-9; %in m^2/s
.B
Area_metal_per_Vol_porous_material = 0.1*100^3; %m^2 platinum/m^3 porous
material
W
Keq2 = 3/101325; %Pa^-1
W
k = 400/60/60; %reaction rate constant, in mol/s/m^2(of noble metal)
Ca = Ca0*(1-X);
W
Cb = Ca0*(theta_b-X);
k_double_prime =
k*R*T*Keq1*Keq2*Pbs/(1+Keq1*Pbs)^2*Area_metal_per_Vol_porous_material;
%mol/s/m^3(catalyst)*1/Pa
phi = (k_double_prime/Dpores)^.5*L;
eta = 1/phi*(exp(phi)-exp(-phi))/(exp(phi)+exp(-phi));
omega = eta*kc/(eta*k_double_prime*L+kc);
r = k_double_prime*Ca*omega; %mol/s/m^3(catalyst)
return
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. I N
E
e) Double thickness of porous layer - more conversion (more catalyst).
V
S S
.B
W
W
W
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. I N
g) Double length of pipes – higher conversion.
V E
S S
.B
W
W
W
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h) Open ended.
Improve reaction rate by increasing T or changing the catalyst to improve surface area to volume
ratio.
Many other answers possible. Equation 4-36 in Fogler gives an equation for calculating pressure
drop in pipes. Whether pressure drop changes significantly or not will depend on the parameters
changed.
The figure below is for a thinner catalyst layer (0.4 um) and more pipes, but with the same total
amount of noble metal. The conversion is slightly higher (71%) than the base case (64%). For
the case shown below, an increase in the total number of pipes (i.e. decrease in the superficial
velocity through each individual pipe) would decrease the pressure drop compared to the base
case. The pressure drop in the base case is assumed to be negligible, so an increase in the total
number of pipes should have no significant effect on the pressure drop.
. I N
V E
S S
.B
W
W
W
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MATLAB REVIEW
The focus of this document is to review common, useful, higher-level Matlab operations
that will be employed on your assignments, such as: ordinary differential equation time
integrators (i.e. ode45 and ode15s, including event functions), curve fitting to a model,
plotting options for x-y plots, and solving sets of nonlinear equations (fsolve). Additional
examples will be made available for future topics. None of these exercises are required
work, but are intended to be a great review and resource for future questions.
Typically, a set of unsteady chemical engineering equations can be cast into the following
form:
df
dt
r r
=
g( f ,t) ,
. I N
r
V E
where time is the independent variable, f is the (unknown) vector of dependent
r
S S
variables, and g is the vector of functions giving the rate-of-change of each dependent
r
variable. Given an initial condition for each dependent variable, f 0 , the equations can be
.B
r
r1
A→ B →C
r2
W
ode solvers. The system is:
r1 = k1 [ A]
r2 = k 2 [B]
and applying the general chemical engineering balance equation on the reactor, we find
that the ode’s governing species are:
d[ A]
= −k1 [ A]
dt
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d[B]
= k1 [ A] − k 2 [B]
dt
d[C]
= k 2 [B]
dt
Since [C] can be expressed in terms of [A] and [B] using mass balances, the third ode is
redundant and need not be followed explicitly. Consider the following initial condition:
[A0] = 1 M, [B0]=[C0] = 0 M. Through two reaction steps, the [A] is converted to [C].
Look at the example file odesintegrate.m. In particular, look at the calling sequence of
the ode solver, which is generally:
[t,f]=ode_solver(@derivative_function_name,[t0,tf],f0,options,param);
where the ode solver can be ode45 or ode15s, for example. The returned values are a
column vector t of time steps, and a matrix f, where each column corresponds to a
variable.
V E
r
df
S S
Basically, you need to pick a solver, set the function that calculates the time derivatives
.B
, set options (such as error tolerances), and pass additional necessary constants.
dt
Options and param may each be [] when using default error tolerances and no additional
W
constants are needed in the derivative function. Note that only the current value of t
(scalar) and the column vector of the current unknowns, f are passed to the derivative
function.
W
W
IMPORTANT: always use column vectors for dfdt and f. This is the format Matlab
expects and use of row vectors leads to errors that you will have to debug later.
Try running each set in the EXAMPLE sequence of odesintegrate.m. (Type “help
odesintegrate” at the Matlab prompt and run each set of parameters in sequence.) This
example sequence illustrates a difference between the performance of ode45 and ode15s.
As k1 is ramped up with a constant k2, the [A] eventually disappears “instantaneously”
relative to the rate of reaction of [B] into [C]. This essentially looks like [A0] =[C0]= 0
and [B0] = 1 case. See Figure 1. Note that the number of time steps that the ode solver
requires to get an accurate result increases as k1 gets much larger than k2. Whenever a
process has two or more vastly differing characteristic rates, the problem can be called
“stiff”.
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. I N
V E
S S
.B
W
W
W
Figure 1. Top: [A0] = 1, [B0] = 0; Bottom: [A0] = 0, [B0]=1; Since k1 >> k2, these
dynamic results are very similar when viewed over the timescale of decay of [B]. Results
obtained with integrator ode45.
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While ode45 is a more accurate time integrator in general, and is a good overall tool,
ode15s handles stiff problems much more quickly; ode15s has better stability properties
and thus can take larger time steps. (This is because ode45 is explicit and ode15s is
implicit. If you would like to more about the inner workings of the time integrators, feel
free to ask.)
Programming Exercise 1:
⎡
df 1 ⎤
⎢ dt ⎥ ⎡
−
1 2
⎤
⎡
f1 ⎤
⎢ df ⎥ =
⎢ ⎥⎢ ⎥
⎢
2 ⎥
⎣
0
−
5
⎦
⎣
f 2 ⎦
⎣
dt ⎦
r ⎡10⎤
f 0 =
⎢ ⎥
⎣10⎦
. I N
V E
Your task is to solve this set of equations numerically in Matlab using ode45. Ensure you
have the correct solution by plotting your numerical expressions for f1 and f2 along with
the analytical expressions:
S S
.B
f1 (t) =
15exp(−
t)
−
5exp(−5t)
f 2 (t) =
10 exp(−5t) .
W
W
Feel free to use the structure of the example file, odesintegrate.m as a template to build
from.
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A priori, you won’t always know how long to run a time integration. Matlab incorporates
“event function” functionality into the various ode solvers to allow for this capability.
The best way to understand how this works is to see an example. Look at
learntouseevents.m.
A set of event functions is attatched to an ode solver with the following options:
options = odeset('Events',@eventfunctionname);
Each event function in the set triggers an event when the function “value” returned is
zero. The event function has the following format:
[value,isterminal,direction] = eventfunctionname(t,f,param);
The event function takes the current value of time, the unknown vector f, and any
additional problem parameters and returns any number of event function values. Each of
. N
the three returned variables, value, isterminal, and direction are column vectors with one
I
entry per event function. For example, if you wanted to have a single event function
terminate integration as soon as f(1) became zero, you would write the code:
V E
function [value,isterminal,direction] = eventfunctionname(t,f,param);
S S
value = f(1); %every zero in the value vector is an event
.B
isterminal = 1; %isterminal =1/0: stop/keep integrating
W
direction = 0; %0/+1 or -1: direction doesn’t matter/does matter
return;
W
See learntouseevents.m for a more sophisticated example of the use of event functions,
W
including recovery of the log of events.
Programming exercise 2:
Using the same solver and code as exercise 1, add an event function that terminates
integration when f2 = 1.
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Trying to put lots of things on the same graph can be a pain, so here is a summary of the
figure creation process.
figure;
or
In the second case, the figure will always have the number n and if figure n exists it will
be replaced unless the hold is on (more on that later). Figure n becomes the “active
figure” on which all plot commands will be placed.
arguments:
. I N
X-Y plots are made by calling the plot command, which may take a variable number of
E
plot(x1,y1,formatstring1,x2,y2,formatstring2,x3,y3,formatstring3,…);
V
S S
See Matlab documentation under “LineSpec” for examples of format strings (or “help
plot”). If several data sets are given in a single plot call, Matlab automatically cycles
.B
through different colors. If you want to have separate plots in separate statements on the
same figure, the “hold on” command must be used, and formats SHOULD be explicitly
specified so you can tell which line is which. For example, try the following series of
commands (copy and paste):
W
W
x = linspace(0,10,101); y1 = sin(x); y2 = cos(x);
W
figure(1); plot(x,y1); plot(x,y2);
figure(4); plot(x,y1,x,y2);
In figure 1, the second plot command over-wrote the first. In figure 2, the second dataset
plotted is by default the same color as the first; in figure 3, this is explicitly corrected and
open circles are used and no line is used. In figure 4, the Matlab defaults automatically
cycle through colors. I recommend you explicitly give figure numbers, so that you don’t
have to close your old figures when doing several runs in a row.
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xlim([xmin,xmax]);
ylim([ymin,ymax]);
title(titlestring);
legend(series1string,series2string…);
or
legend({series1string,series2string,series3string…});
grid on;
. I N
V E
This should cover most plotting needs you will have. Advanced options are available.
Look up the Matlab “help plot” for details.
Programming exercise 3:
S S
.B
Using the results of exercise 1 or 2, plot f1 with red upward facing triangles (no line) and
W
f2 with a blue dashed line (no symbol). Ensure the minimum x and y values on the plot
are zero, and all the data are visible in the plotted range.
W
W
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The Matlab “fit” function is a versatile tool for fitting parameters to user-specified
models. This example will show you how to fit some noisy data to a sine function.
x = linspace(0,2*pi,101)';
f = sin(x+0.1*randn(size(x)))+0.1*randn(size(x));
plot(x,f);
model=fittype('A*sin(B*x+C)+D','ind','x');
declares a 4-parameter model based on the sine function and declares x to be the
independent variable. Next you should guess the parameters in the order they appear
from left to right:
. I N
initial_guess=[1.00,1.00,0,0];
V E
Note that we guessed our values as those that you should get if there were no noise in the
data. Finishing up, call:
S S
.B
options=fitoptions(model);
set(options,'StartPoint',initial_guess);
fresult = fit(x,f,model,options);
W
The values of A, B, C, and D are stored in the struct fresult. The resulting parameters can
W
be viewed as a whole by typing:
fresult
W
and the two plots can be compared by using the model directly as if it were a function.
Try typing:
plot(x,f,x,fresult(x));
Individual parameters from the fit can be extracted with struct “dot” notation. For
example, to see parameter A type
fresult.A
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Programming Exercise 4:
Collect and save the f1 output you get from exercise 1. Add some noise to it, using the
command:
f1 = f1 + (0.1*randn(size(f1)));
Fit a 4-parameter model to fit f1(t) = Aexp(Bt) + Cexp(Dt). Do you recover the
coefficients A, B, C, and D that you expect?
. I N
V E
S S
.B
W
W
W
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Matlab has the ability to solve nonlinear systems of equations using fsolve, where
r r
0 = g ( x) .
This could be interpreted as directly finding the steady state of the equation
r
df r r
= g( f , t) .
dt
The calling sequence of fsolve is very similar to the use of ode integrators. The main
difference is that instead of supplying a function to calculate the derivatives, you supply a
function to calculate the right-hand-side of the equation, g. When g is not zero, this is
also called the residual.
. I N
x = fsolve(@gfun,x0,options,param);
V E
Where x0 is the initial guess, param are additional constants needed by the g function,
and gfun is the gfunction:
S S
.B
[y,Jacobian] = gfun(x,param);
gfun returns the value of each of the g(x) functions in y. When all the entries in the
W
column vector y are zero, the system is solved with the current iterate of x.
W
The Jacobian matrix is an expression that contains the rate of change of each of the g
functions with respect to each of the parameters x (as in Newton iteration). Entries are
given by:
∂g
J ij = i .
W
∂x j
The Jacobian matrix is an optional returned value in gfun. In general, Matlab will use a
numerical approximation of the analytical Jacobian. The user specifically mentions that
an specified analytical Jacobian will be given with the statement:
options = optimset('Jacobian','on');
The use of fsolve is demonstrated in the example file multiplefsolve.m. Given a perimeter
and area, this function finds the length and width of an appropriate rectangle if one exists:
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g1 (L,W ) = 2L + 2W − P
and
g 2 (L,W ) = LW − A ,
where L = length, W = width, P = perimeter, and A = area. Notice that the g functions
must be rearranged so that they are zero when satisfied by appropriate L and W.
Programming exercise 5:
Following the example of multiplefsolve.m, make a program that finds the height and
radius of a cylinder with a given area and volume. Multiple solutions may exist! Verify
that your program gives you R = 1 and H = 1 when Area = 4*pi and Volume = pi with an
appropriate initial guess.
. I N
V E
S S
.B
W
W
W
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Use meaningful names for variables. If you have a list of 10 different chemical species
stored in x(1), x(2)…x(10), you shouldn’t be using them in that form in your reaction
equations. Consider renaming them as soon as you enter the function or declare
descriptive names equal to your integer indices, e.g.
Cl = 1;
Na = 2;
NaCl = 3;
x(Cl)*x(Na);
x(1) * x(2);
. I N
V E
Go for simplicity and clarity before going for elegance. Colon notation is an effective
way to make Matlab programs more compact, but for loops are much more intuitive. Use
S S
for loops if colons give you trouble. Furthermore, in general, several simple steps are
easier to understand than one long, complicated step.
.B
Watch out for the differences between matrix and element-wise operations. This
W
leads to common mistakes. Most functions, such as sin() and exp() can accept a matrix of
any size rather than a single value. They operate on each matrix element individually,
W
returning the sin() or exp() of each element, respectively. However, whenever you use
the operations (*,/) and the objects being multiplied/divided are vectors or matrices, be
W
sure to know the difference between (*,/) and (.*,./). The first uses matrix multiplication
and the second does element-wise operations, operating on corresponding entries. If this
gives trouble, feel free to use for loops to operate on one value at a time.
Learn to use the Matlab debugger. Programs usually fail on the first try. Matlab has a
useful debugger, where you can put breakpoints in the code, examine variable values
during execution, and even execute any additional operations from the command line
(such as make plots). As an alternative to placing a breakpoint, the “keyboard;”
command will do the same thing. To exit debug mode at the command line, type
“return;”. On the command line, “who” is a useful command that displays the names of
all the variables that are known at this point in the code. Each one can be inspected or
operated upon.
Use semicolons. If semicolons are omitted at the end of a line, more output is sent to the
screen. In the case of large matrices, it can be a startlingly large amount.
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Use functions rather than scripts. A function takes input and gives output; this makes
it easy to build a code as a group of working parts with well-defined interfaces. If a
function can’t change its input to mess up the calling program. A script works at the
same level as the regular Matlab prompt. In a script, all variables are effectively global,
and thus from run to run things might change depending on what is stored in all current
values of the variables. Also, if you run two different scripts, they could use the same
variable names and operations and results can get mixed up.
. I N
V E
S S
.B
W
W
W
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In-Out+Production=Accumulation
XA =
N A0 − N A
N A0
. I N
N A = N A0 (1 − X A )
V E
Thermodynamics
Suppose ZZZX
A + B YZZZ 2C
k1
S S
.B
k −1
− ΔG RT
Ke = e
ΔG = ΔG °f , products − ΔG °f ,reactants
[ B ][C ] W
Kc =
[ A] W
has units. You need to use standard states, such as 1M, to make it
dimensionless.
Enzyme Catalysis
W
without enzyme
with enzyme
Energy
P
Reaction Progress
Figure 1. Energy diagram for a reaction with and without enzyme.
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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
. I N
Rate Constants
V E
k (T ) = Ae − Ea RT
S S
Given k1 and k2, you can calculate k and a different temperature.
CSTRs .B
V=
FA0 X A
−rA W
W
W 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:
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Exam1 Review
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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
Solve given Cˆ A = 0 at tˆ = 0
. I N
Cˆ A =
1
1 + Da
( ˆ
1 − e− (1+ Da )t )
V E
Tanks in series: 1st order reaction
C A, n =
C A,0
S S
(1+ Da )
.B
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.
. I N
Selectivity
V E
CSTR
S S
φinst .B
W Φ overall ΔC A
W
W
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 Åproperty of a dirac delta function
. I N
0
For a CSTR, E (t ) =
e−t τ
V E
τ
S S
Example 1
z .B
W L
FA0
W FA, FB, FC
A ⎯⎯ r1
→ B ⎯⎯
r2
→C
r1 = k1C A r2 = k2CB
W
Figure 4. Schematic of a PFR with inflow of A and outflow of A, B, and C.
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
ν0
z [ = ] time, call it τ
. I N
This is the time it takes for something to flow to the end of the reactor (of length z).
ν0
Axs
G
= V velocity
V E
dCB
dτ
+ k2CB = k1C A0 e− k1τ
S S
Integrating factor: e 2
d
kτ
W
kC
0 = 1 A0 + φ
k2 − k1
W
Initial condition: z=0, CB=0 B
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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find
A
B C
τ∗ τ
dCB k1C A0
( ) . N
Figure 5. Graphs of flow rates of A, B, and C as a function of residence time.
I
dτ
=
k2 − k1
−k1e− k1τ * + k2 e− k2τ * = 0
τ* =
k
ln 1
k2 W
k1 − k2
W dA( x)
W
L’Hopital’s rule: lim
A( x) 0
x → x* B ( x )
= do lim
0 x → x*
dx
dy
dB ( x)
dx
dx
Find τ* for k1=k2
1
k1 1 1
lim τ * = lim = =
k1 → k2 k1 → k2 1 k2 k
A L A z
τ * = xs τ = xs
ν0 ν0
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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
RT
( Ftotal = n , ν = V )
. I N
ν = Ftotal
E
−1
= Ftotal Ctotal
P
Ftotal = FA + FB
FA = C Aν = y A Ftotal
S V
dFA
dV
dFB
= − ky ACtotal = − k
FA
FA + FB RT
FA
P
P .B S
dV
= +2ky ACtotal = +2k
W
FA + FB RT
W
If P or T changes, you need other equations.
W
Derivation of E(t) for a CSTR
N 0δ (t )
No reaction:
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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
=
. I N
⎛ −t ⎞
C = C0 exp ⎜ ⎟
⎝τ ⎠
V E
E (t ) = ∞
C
∫ Cdt S S
∞
0
∞
∫ Cdt = ∫ C e
−t
τ
dt = C0 ⎡ −τ e
−t
τ
∞
.B
⎤ = C ⎡ −τ ( 0 − 1) ⎤ = C τ
0 0
0
−t −t
⎣⎢
W ⎦⎥ 0 0 ⎣ ⎦ 0
Ce τ e τ
E (t ) = 0
C0τ
=
τ W
Long-chain approximation
W
ZZZ
E + S YZZ1
X
Z ES ⎯⎯
k k2
→P+ E
k −1
tRNA ⎯⎯
→E k3
E ⎯⎯
k4
→ Deactivate
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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
. I N
V E
S S
.B
W
W
W
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There are 4 problems. Pick any 3 of these problems to do and turn in. (If you turn in
solutions to 4 problems, we will not count the problem where you earned the lowest
score.) Please turn in your solution for each problem separately. Write your name on
every blue book or sheet of paper you turn in.
Problem 1. (100 points) A reactant stream is split to feed, in parallel, two CSTRs, one of
which is twice the volume of the other. The effluents from the two CSTRs are combined.
The reaction of interest follows a first-order rate law.
a) (50 points). How should the feed stream be split in order to maximize the total
reactant conversion in the combined effluent from the two CSTRs?
Small
CSTR . I N
V E
S S
.B
Feed Effluent
Big CSTR
W
W
W
b) (50 points). Using the same feed, what overall conversion would be obtained by
placing these same two CSTRs in series (i.e. the effluent of the first is the feed of
the second)? (Consider both possible topologies – one where the large CSTR
feeds the smaller, and one where the small CSTR feeds the larger.) Is this
conversion superior or inferior to the best case calculated in a)?
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Problem 2. (100 points) An appealing partial solution to the greenhouse gas problem is
to convert biomass into liquid fuels. Most of biomass is composed of linked C6 sugars
(C6H12O6) and C5 sugars (C5H10O5), which can be broken down by an enzyme secreted
by fungi. Ideally, the sugars could then be converted into ethanol or other liquids in
subsequent reactions.
This mechanism is proposed for the enzymatic breakdown:
C11H22O11 + Enzyme Æ Complex (reaction 1)
Complex Æ Enzyme + C6H12O6 + C5H10O5 (reaction 2)
where [C11H22O11]0 and [Enzyme]0 are the initial concentrations added to the mixture, i.e.
. N
(moles added / volume of solution), not necessarily the actual concentrations of these
I
species in the beaker when the reaction is running, since some of the enzyme will exist in
the form of the complex.
V E
(a) (20 points) Is the observed rate law (Eqn 3) consistent with the mechanism shown
S S
above? If so, give an expression for b in terms of k1, k-1, and k2. If not consistent, explain.
Suppose we could tether 10-9 mole of enzyme within a 4 mm diameter porous particle
.B
without affecting the rate law (i.e. r is given by Eqn. 3). The diffusivity inside the porous
particles is 10-10 m2/s. In the bulk fluid D = 7x10-10 m2/s. Suppose we then filled a packed
W
bed reactor (internal diameter 2 cm, length 30 cm) with many particles like this, and
flowed an aqueous solution of C11H22O11 through the reactor at rate of 1 liter/minute. The
W
void fraction of the packed bed φ=0.4. For concentrations of C11H22O11 below 0.5 M, the
viscosity and density of the solution is essentially the same as that of water.
W
(b) (30 points) Write an equation for the Thiele modulus for this system, as a function of
[C11H22O11]. Over what range of [C11H22O11] is it reasonable to neglect diffusive
transport limitations?
(c) (30 points) If [C11H22O11] is always in the range where transport limitations are
negligible, what differential equation(s) should be solved to compute the conversion?
What Matlab program would you use to solve the equation(s) numerically? Write the
differential equation(s) in the form dY/dt = F(Y) required by the Matlab solvers.
(d) (20 points) Write (but do not attempt to solve) the differential equation(s) with
boundary conditions that would have to be solved to compute the effectiveness factor Ω
if [C11H22O11]bulk had a value outside the range specified in part (b). Are you missing any
data needed to calculate Ω?
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. I N
A) (60 points) Determine Kd, kon, and koff. Are these data self-consistent?
V E
B) (40 points) In a separate experiment, soluble protein (2 nM) and ligand (0.1 nM)
S S
are mixed. At equilibrium, what fraction of ligand is complexed with the protein?
At what time following mixing will 95% of this equilibrium value be attained?
.B
W
W
W
Problem 4. (100 points total) “Clean Coal” technology is based on first converting the
coal into syngas (an H2 + CO mixture). The syngas can then be purified and used to make
clean synthetic fuels, or to generate electricity (with CO2 sequestration). The largest and
most expensive reactor in a “clean coal” plant is the gasifier. The main reactions are:
r1 = k1(T)[O2]2[H2]/([H2O] + a[H2])
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The final 1100 K output stream coming out of the gasifier has no carbon and a negligible
I N
concentration of O2(g), but large concentrations of CO, H2, and steam. Assume that the
.
heat capacity of the feed stream is 3 MJ/ton-Kelvin and that the heat capacity per ton
E
does not change significantly with temperature or the change in composition through the
reactions. The process is carried out at Ptotal=40 bar. The input stream is at 700 K, and
V
consists of 120 tons per hour of C(s), 120 tons per hour of steam, 64 tons per hour of O2,
and 0.02 tons per hour of H2.
S S
.B
(a) (20 points) What is the molar flow rate of CO, H2, and H2O at the output? What is
the volumetric flow rate of the output?
W
(b) (25 points) How much heat must be transferred per second to maintain the output
W
at 1100 K? Is the heat flowing into or out of the reactor? How could you adjust
the composition of the feed to reduce the amount of heat transfer required, while
W
still maintaining the same Carbon feed rate and output temperature?
(c) (30 points) Write the equation(s) that should be solved to compute the conversion
of O2 in the adiabatic PFR, V1=1 m3, in a form that can be solved numerically by
Matlab. What Matlab program would you use to solve these equations?
(d) (25 points) What CSTR reactor size V2 is required so that 99% of the initial feed
O2 and 99% of the initial feed carbon will be consumed by the time the mixture
leaves the isothermal (1100 K) CSTR? Hint: How much carbon was consumed by
reacting with O2? So how much carbon must be consumed by reaction 2?
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A ⎯+⎯⎯→ B
H 2O
a) (20 points) What is the steady-state fractional conversion of A if the feed rate is
0.3 L/sec and the feed concentration CA,o = 0.12 mol/L?
b) (10 points) If the feed rate suddenly drops to 70% of its original value and is
maintained there, what is the fractional conversion of A after 60 minutes, and
what is the new steady state fractional conversion?
. I N
case b) relative to case a)?
V E
c) (10 points) What is the ratio of the steady-state productivity (moles/time) of B for
S S
.B
Problem 2. (30 points) W
W
W
A 600 L tank reactor gives 75% conversion for a first order irreversible reaction.
However, the paddle turbine motor is underpowered and so the tank is not well stirred. In
fact, a pulse-tracer experiment to determine the residence time indicates that
approximately 400 L of the tank may be considered as a dead volume that does not
interact appreciably with the input or output streams. If you replace the stirrer with one
sufficiently strong to obtain complete mixing throughout the reactor volume, what
conversion will be obtained?
The cellulose oligomers are introduced as a 20 wt% slurry in liquid water; 60 grams of
the slurry are introduced every second. At this high temperature, it is a good
approximation to assume all the species in the reactor are in the gas phase. The reaction
rate law has been measured at 600 K under these conditions to be:
r = k [CnH2nOn(g)] / {1 + a [CO(g)]}
. I N
The pressure in the reactor is 20 atm. There is no significant pressure drop in the reactor.
The cross-sectional area inside the reactor is 10 cm2, and the reactor is 3 m long.
V E
Write the differential equation(s) that would have to be solved to predict the
format:
S S
moles/second of H2 coming out of the reactor. Write the equation(s) in the standard ODE
dY/dz = f(Y)
.B
W
where Y(z) are the unknown(s) you want to compute, and there are no other
unknowns on the right hand side of the equation(s). Please do not attempt to solve the
equation(s).
W
W
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Solutions.
Problem 1.
a) For first-order reaction kinetics
10000 L
2.5 × 10-3 min −1×
Da kτ 0.3L / sec =0.58
XA = = =
1 + Da 1 + kτ 1 + 2.5 × 10-3 min −1× 10000 L
0.3L / sec
b) Consider the non-steady state design equation for CSTR, where we can have
dN A
FA0 − FA + rAV =
dt
Since in liquid phase with constant density, we have
dC A
C A0 − C A - kC Aτ = τ
dt
or equivalently
dCA 1 + kτ C
+ CA = A0
dt τ τ
L/min)=793.7 min
. I N
with the initial conditions CA,t=0=(1-0.58)×0.12 mol/L=0.05 mol/L, new τ=10000L/(0.7×0.3*60
C A (t ) =
C A0
{1 − exp[−
1 + kτ
V E
t ]} + C A, t = 0 exp(−
1 + kτ
t)
1 + kτ
Therefore the conversion at time t is
τ
S S τ
X A (t ) = 1 −
1
1 + kτ
{1 − exp[−
.B
1 + kτ
τ
C
t ]} − A, t = 0 exp[−
C A0
1 + kτ
τ
t]
W
The new steady state fractional conversion is
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Problem 2.
We know for first order reaction, conversion XA has the following relation with rate constant k,
CSTR reactor volume V and volumetric flow rate v
V
k
XA = v
V
1+ k
v
When we have a dead volume (denoted as subscript 1) which does not interact with the input and
output streams, we can deduce this amount of volume from the overall reactor volume.
V1
k
X A1 = v
V
1+ k 1
v
We are told V1=600L-400L=200L, XA1=0.75, therefore we can calculate
k X A1
v
==
V1 (1 - X A1 )
=0.015.
. I N
Then for the well-stirred reactor, V=600L
V
k
V E
XA = v =0.9
1+ k
S
V
v
S
.B
W
W
W
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Problem 3.
For a PFR reactor, the design equation is
dX celluose -r
= S celluose
dz Fcelluose, in
Also
P 20 atm
. I N
y P
[cellulose]in = cellulose,0 =
20%
720 gram/mol 20 atm
V E
= 2.52 mol/m3
RT (
20%
+
1 − 20
720gram/mol 18gram/mol
%
S
) 8.314J/(mol K) × 600K
S
.B
where ycellulose,0 is the molar fraction of cellulose in the inlet.
W
In this problem, since the gas phase reaction creates more molecules, the volumetric flow rate is
not a constant.
W [cellulose]
W - rcelluose = k
1 + a[CO]
where the concentrations should be expressed (constant pressure and temperature are assumed)
(1 - X)
[cellulose] = [cellulose]in
(1 + εX)
and
24X
[CO] = [H 2 ] = [cellulose]in
(1 + εX)
Here ε=(24+24-1)ycellulose,0=47*0.0062=0.292.
Now the final molar flow rate of H2 is
vfinal[H2]=24vin[cellulose]inXf
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Problem 2: 30 points
A surface-catalyzed reaction follows Rideal-Eley kinetics as follows:
⎯⎯⎯
kA
A + S ←⎯⎯ → AS
⎯
k− A
. I N
AS + A ⎯⎯ → A2 + S
E
k1
Assuming that:
adsorption of A is at rapid equilibrium
reaction of AS with A is rate-limiting .B S
W
desorption of A2 is very rapid
W
Derive the steady-state rate law for production of A as a function of the concentration of
2
W
A and the total initial reactive site density So .
Problem 3: 35 points
It is desired to make a product X-Y via this reaction:
X-OH + Y-H → X-Y + H2O
o o
An equimolar feed of liquid X-OH and Y-H at 25 C are fed to a CSTR. At 25 C, where all 4
material species are liquids, the heat of reaction ∆Hrxn=-200 kJ/mole, and the heat capacity of
o
each liquid-phase species is 4 kJ/(kg C ). The molecular weight of X-OH is 150 g/mole, and the
molecular weight of Y-H is 100 g/mole. The temperature inside the reactor (T) is controlled by
putting the reactor in thermal contact with a fluid flowing over the outside of the reactor at
temperature Ta. To a good approximation, the heat transfer rate (Q, in watts) from the fluid
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flowing over the outside the reactor to the contents of the reactor is given by the linear
expression: Q = UA(Ta-T)
o
a) If the reaction is carried out with the reactor at steady-state at the inlet temperature of 25 C, is
T greater than, less than, or equal to Ta? (5 points)
o
b) When running the reactor at T = 25 C to 50% conversion, the productivity is unacceptably
low. To try to accelerate the reaction, it is decided to increase the steady-state reactor
o
temperature to T = 105 C. At this temperature, all of the H2O formed evaporates, but the
o
other species are still liquids. The heat of vaporization of H2O at 105 C is +40 kJ/mole.
o o
When T=105 C, the reaction runs to 50% conversion 10x faster than it did at 25 C, so we
o
increase the flowrates until the reactor is making 10x as much product as it did at 25 C (still
at 50% conversion). When we achieve the new steady-state high-productivity operation at
o
. N
105 C, will the magnitude of Q (i.e. |Q|) be larger, smaller, or the same as it was when we
I
were operating at 25 C? At this steady-state condition, is T greater than, less than, or equal
to Ta? (20 points)
V E
S S
c) Since operating hot improved our productivity, but conversion is still pretty low, the operator
.B
o
tries to improve things by cranking up the temperature, preheating the inlet streams to 185 C
and increasing Ta. For good measure the operator simultaneously cranks up the reactor
W
pressure from 1 bar to 100 bar; at this high pressure all the species remain as liquids. (The
W o
reactor is safe at this condition, and even up T = 300 C.) Curiously, the conversion and
W
productivity of the reactor do not increase under these severe conditions, instead they
decrease. Propose an explanation for this experimental observation. (5 points)
d) Your manager gives the operator who turned up the temperature (without doing any
calculations first) a formal reprimand, saying the operator is probably lucky
that the conversion went down instead of increasing. Why do you think the
manager was happy that conversion was low instead of increasing a lot? (5 points)
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10.37 Exam 2
25 April, 2007
100 points
Problem 1: 35 points
A protein and ligand bind reversibly with K d = 10 nM . The association rate constant
kon = 2x10 4 M−1s-1 . The two species are mixed at an initial protein concentration of 3 nM
and an initial ligand concentration of 0.2 nM.
a) At equilibrium, what fraction of the ligand will be complexed with protein? (15 points)
b) At what time will the fraction of ligand in complex reach 95% of the equilibrium
value? (20 points)
Justify any assumptions you make to simplify equations.
P + L ←→ C
k off [P] eq [L] eq
Kd = =
k on [C] eq
. I N
Using a batch reactor mole balance and looking at the reaction stoichiometry, it is easy to
W
([L]0 + [P]0 + K d ) ± ([L]0 + [P]0 + K d )2 − 4[P]0 [L]0
[C]eq =
W 2
=0
Reject the positive root, it is too large (larger than the initial amount of ligand and
protein).
[C]eq = 0.0456nM
[C]eq
= 0.228 = 23%
[L]0
At this point, it is interesting to look at different approximations to the expression.
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[L]0 [P]0
[C]eq = 0.462nM
K d + [P]0
[C]eq
= 0.231 = 23%
[L]0
Bad Approximation: [L]0 >> [C]
Kd ≈
([P]0 −[C]eq )([L]0 )
[C]eq
[L]0 [P]0
[C]eq = = 0.0588
K d + [L]0
[C]eq
= 0.294 = 29%
[L]0
The error in [C]eq of the bad approximation is about 30% of the true answer, whereas the
good approximation is only off by about 1%.
d[C] W
Rearrange and solve using the integrating factor:
+ [C](k on [P]0 + k off ) = k on [L]0 [P]0
dt
dt
[ W ] [
([C]exp (kon [P]0 + koff ) t ) = kon [L]0 [P]0 exp (kon [P]0 + koff ) t ]
([C ] exp [(k on [P]0 + k off ) t ]) = k on [L]0 [P]0 exp ((k on [P]0 + k off )t ) + I .C.
(k on [P]0 + k off )
[C] =
[ L ]0 [ P ] 0
[
+ I.C.exp − (k on [P]0 + k off ) t ]
([ P]0 + K d )
Using the initial condition, [C](t = 0) = 0, we find the integration constant to be:
[L]0 [P]0
I.C. = −
([P]0 + K d )
Hence,
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[L]0 [P]0
[C](t) = {1− exp[− (k ]
[P]0 + k off ) t }
([P]0 + K d )
on
In order to find the point at 95% of the equilibrium value, rearrange and solve for the
time when [C]/[C]eq=0.95:
[C](t*)
[
= 0.95 = {1− exp − (k on [P]0 + k off ) t * } ]
[C]eq
[
0.05 = exp − (k on [P]0 + k off ) t * ]
− ln(0.05) − ln(0.05) 3.00
t* = = = = 11500s
(k on [P]0 + k off ) (kon [P]0 + kon K d ) 2x10 nM s [3nM +10nM ]
N
−5 −1 −1
t* = 11500s ≈ 3.2h
E . I
S V
Problem 2: 30 points
.B S
A surface-catalyzed reaction follows Rideal-Eley kinetics as follows:
→
kA
A + S ← AS
k− A
W
AS + A
k1
→ A2 + S
W
W
Where A and A2 are in the gas phase, S is a reactive site on the surface, and AS is a
molecule of A adsorbed to a reactive site.
Assuming that:
• adsorption of A is at rapid equilibrium
• reaction of AS with A is rate-limiting
• desorption of A2 is very rapid
Derive the steady-state rate law for production of A2 as a function of the concentration of
A and the total initial reactive site density So .
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C kA
rAd = k A C A C v − AS where K A =
KA k−A
rs = k1C AS C A
rAd
Adsorption is at rapid equilibrium, so ≈0
kA
C AS
C ACv = ⇒ C AS = K A C A C v
KA
So
S o = C v + C AS = C v + K A C A C v ⇒ Cv =
1 + K AC A
. I N
Given that the surface reaction is the rate limiting step, and the stoichiometric coefficient
rA' 2 = rs = k1C AS C A = k1 K AC v C A2 =
k1 K A S o C A2
V E
1 + K AC A
S S
Problem 3: 35 points
.B
W
It is desired to make a product X-Y via this reaction:
X-OH + Y-H → X-Y + H2O
W
An equimolar feed of liquid X-OH and Y-H at 25oC are fed to a CSTR. At 25oC, where
W
all 4 material species are liquids, the heat of reaction ∆Hrxn=-200 kJ/mole, and the heat
capacity of each liquid-phase species is 4 kJ/(kg Co). The molecular weight of X-OH is
150 g/mole, and the molecular weight of Y-H is 100 g/mole. The temperature inside the
reactor (T) is controlled by putting the reactor in thermal contact with a fluid flowing
over the outside of the reactor at temperature Ta. To a good approximation, the heat
transfer rate (Q, in watts) from the fluid flowing over the outside the reactor to the
contents of the reactor is given by the linear expression:
Q = UA(Ta-T)
a) If the reaction is carried out with the reactor at steady-state at the inlet
temperature of 25oC, is T greater than, less than, or equal to Ta? (5 points)
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For an exothermic reaction, to maintain the products at the same temperature as the
reactants one must remove heat. So T must be greater than Ta, i.e. Ta must be below
room temperature.
. I N
the magnitude of Q (i.e. |Q|) be larger, smaller, or the same as it was when we
were operating at 25oC? At this steady-state condition, is T greater than, less than,
or equal to Ta? (20 points)
V E
S S
If the reaction ran 100% to completion, it would release (200 kJ/mole)(1 mole/0.25
.B
kg entering the reactor)=800kJ/kg entering the reactor. Since we only have 50%
conversion, the chemical heat release is half as much, 400 kJ/kg. Heating the feed
from 25 C to 105 C requires: (80 degrees)(4 kJ/kg) = 320 kJ/kg entering the reactor.
W
Evaporating the water formed by the reaction requires an additional (40 kJ/mole
H2O)(0.5 mole H20/ 0.25 kg entering reactor) = 80 kJ/kg. Since the heat release and
W
the heat required to warm up the mixture and evaporate the water balance, Q=0 now.
In contrast, when we ran the reactor at 298 K, we had to remove heat at a rate of 200
W
kJ/kg. So the magnitude of Q is much lower now than before, and T should
approximately equal Ta.
c) Since operating hot improved our productivity, but conversion is still pretty low,
the operator tries to improve things by cranking up the temperature, preheating
the inlet streams to 185oC and increasing Ta. For good measure the operator
simultaneously cranks up the reactor pressure from 1 bar to 100 bar; at this high
pressure all the species remain as liquids. (The reactor is safe at this condition,
and even up T = 300oC.) Curiously, the conversion and productivity of the reactor
do not increase under these severe conditions, instead they decrease. Propose an
explanation for this experimental observation. (5 points)
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It is possible that we are running into equilibrium limitations on the reaction. For
exothermic reactions, Keq decreases with increasing temperature. So if we are
equilibrium limited at high T, we would expect the conversion to decrease as T
increases. (Note that by increasing the pressure so dramatically, the operator
prevented most of the H2O from evaporating, hence the concentration of H2O in the
liquid phase is probably much higher now than it was in the 105 C case where the
water evaporated; this contributes to the equilibrium limitation).
d) Your manager gives the operator who turned up the temperature (without doing
any calculations first) a formal reprimand, saying the operator is probably lucky
that the conversion went down instead of increasing. Why do you think the
manager was happy that conversion was low instead of increasing a lot? (5 points)
Exothermic reactions can “run away” if T goes high enough, i.e. past a certain point,
I N
the steady-state conversion will suddenly jump from a low number to a very high
.
conversion, releasing essentially the whole exothermicity, and jumping the T to a
V E
temperature above the safety limits of the reaction vessel. In the present case, if the
reverse reaction were negligible the reaction would release 800 kJ/kg, enough to
increase the temperature inside the reactor by up to 200 degrees, so it could have
S S
exceeded the T=300 C safety limit. The results could have been fatal to the operators
or anyone else nearby. But fortunately in this case it was lucky that high conversion
.B
was not achievable due to the small value of the equilibrium constant.
W
W
W
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Go over the first problem in PS7 to review the ligand/receptor binding kinetics and
the first problem in PS8 to review the surface reactions/catalysis kinetics.
Problem 1.
The irreversible liquid phase reaction A →R + S is carried out in a CSTR. The reaction is
first order in A. The feed stream is available at a temperature of 298 K.
-4 -1
k = 1.7 x 10 s at 298 K.
3
Ea = 41.87 x 10 kJ/kmol
3
ΔHR(298) = -167.5 x 10 kJ/kmol
3
CA0 = 2.0 kmol/m (Feed is pure A)
V = 0.5 m
3
3
. I N
ρ = 1050 kg/m
Cp = 4.19 kJ/kg/K
V E
S S
These values can be considered to be constant over the used interval of concentration and
temperature. The CSTR is made of carbon steel and weighs 800 kg.
Cp,steel = 502.4 J/kg/K
Calculate:
.B
a) Conversion and heat duty for an isothermal reactor operating at 298 K.
W
b) Conversion and reactor temperature for an adiabatic reactor with inlet temperature
of 298 K.
W
c) Conversion and preheating temperature for an adiabatic reactor with a reactor
temperature of 363 K.
W
d) Conversion and heat duty if the reactor is operated non-adiabatically without
preheating and at a temperature of 363 K.
Problem 2.
Consider an organism which follows Monod equation of growth with μmax = 0.5 h-1 and Ks = 2 g/L.
a) In a continuous perfectly mixed vessel at steady state with no cell death, if the substrate
concentration in the feed is Sfeed = 50 g/L, the yield Y = 1 (g cells / g substrate), what
dilution rate D gives the maximum volumetric productivity?
b) For the same dilution rate as part (a) using tanks of the same size in series, how many
vessels will be required to reduce the substrate concentration to less than 1 g/L?
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. I N
V E
S S
.B
W
W
W
. I N
V E
S S
.B
W
W
W
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. I N
V E
S S
.B
W
W
W
. I N
V E
S S
.B
W
W
W
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