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Chemical Kinetics and Reactor Design Course Review: 1 Stoichiometry
Chemical Kinetics and Reactor Design Course Review: 1 Stoichiometry
Course Review
James B. Rawlings
Department of Chemical Engineering
University of Wisconsin
1
3 Rate Expressions
r = k(T )f (cj ’s)
Arrhenius expression for k: k(T ) = k0 e−Ea /RT , Ea is the ac- d(cj VR )
BATCH = Rj VR (1)
tivation energy, always positive. How does raising temper- dt
dcj
ature affect reaction rate? What is f (cj ’s) for a sequence of constant volume = Rj (2)
dt
elementar y steps. What is the difference between a mech-
d(cj VR )
anism and an overall stoichiometry. Quasi-steady-state as- SEMI-BATCH = Qf cjf + Rj VR (3)
dt
sumption, equilibrium assumption and rate limiting step.
d(cj VR )
CSTR = Qf cjf − Qcj + Rj VR (4)
Langmuir Isotherms (chemisorption) dt
dcj 1
constant volume = (cjf − cj ) + Rj (5)
dt τ
-*- A · X
A+X ) steady state cj = cjf + Rj τ (6)
KA cA c m ∂cj ∂(cj Q)
cA = PFR = − + Rj (7)
1 + KA c A ∂t ∂V
d(cj Q)
Hougen-Watson rate expressions Deciding which mecha- steady-state = Rj (8)
dV
nism best explains rate data. dcj
constant density, = Rj (9)
dτ
d
Z Z
cj dV = Q0 cj0 − Q1 cj1 + Rj dV , j = 1, . . . , ns
dt V V
dU
= m0 Ĥ0 − m1 Ĥ1 + Q̇ − Ẇs
dt
dT X
BATCH VR ρ ĈP = − ∆HRi ri VR + Q̇ (10)
dt i
dT X
CSTR VR ρ ĈP = − ∆HRi ri VR + Q̇
dt i
X
+ cjf Qf (H jf − H j ) (11)
j
PFR
dT X
(steady state) Qρ ĈP = − ∆HRi ri + q̇ (12)
dV i
2
Q̇ Ẇ
cj
cjs
A
V
m1
m0 D
E1
E0
cj1
cj0
T
cj
Figure 1: Reactor volume element.
R Te
1 460
cej
0.9 440
r extinction point
0.8 420 r extinction point
0.7
400
0.6
380 B C
x 0.5 T (K)
360
0.4
340
0.3
0.2 320
r ignition point Figure 4: Expanded views of a fixed-bed reactor.
0.1 r ignition point 300
0 280
0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 30 35 40 45
τ (min) τ (min)
5. reaction of adsorbed reactants to adsorbed products
(surface reaction)
Figure 2: CSTR steady-state multiplicity, stable and unsta-
ble steady states, ignition, extinction, hysteresis. 6. desorption of adsorbed products
1 400
7. diffusion out of pores
380
x(t) 8. mass transfer from catalyst to bulk fluid
360
320
Simultaneous Reaction and Diffusion
T (t) 300
∇2 cA + RA = 0
0 280
0 100 200 300 400 500 600
time (min) 1st order reaction, spherical pellet:
1 ∂ 2 ∂c
Figure 3: CSTR oscillations. r − (3Φ)2 c = 0
r 2 ∂r ∂r
3
dNj
Φ = 0.1 = Rj (16)
1 dV
dT X 2
0.8 Φ = 0.5
Qρ Ĉp = − ∆HRi ri + U o (Ta − T ) (17)
dV i
R
" #
0.6 dP (1 − B ) Q (1 − B )µf 7 ρQ
c =− 150 + (18)
dV Dp B3 A2c Dp 4 Ac
0.4 Φ = 1.0 Rj = (1 − B )R e jp (19)
X X
0.2 ∆HRi ri = (1 − B ) ∆HRi reip (20)
Φ = 2.0 i i
0
P
0 0.5 1 1.5 2 2.5 3
ε = 1 − ρb /ρp , Q= j Nj /c(P , T )
r
0.1 1 10
0.001
0.01 0.1 1 10 100
ce (t) = cf (t 0 )p(t − t 0 )dt 0 , cf (t) = 0, t ≤ 0 (21)
Φ Φ 0
Step response, impulse response for CSTR, PFR, n CSTRs,
Figure 5: Effectiveness Factor Versus Thiele Modulus: Effect PFR with dispersion.
of Geometry and Reaction Order. Segregated reactor, maximally mixed reactor.
1 I1 (2Φ)
Cylinder η = (14)
Φ I0 (2Φ) 7 Parameter Estimation
tanh Φ probability review. Normal distribution, mean, variance.
Slab η = (15)
Φ !
1 1 (x − m)2
p(x) = √ exp − (22)
Table 2: Effectiveness factor versus Thiele modulus for the 2π σ 2 2 σ2
sphere, semi-infinite cylinder, and semi-infinite slab. 1
1 T −1
p(x) = exp − (x − m) P (x − m)
(2π )n/2 |P |1/2 2
4
10
c0 c1 c2 c3
8
τ1 τ3
τ2
6
1
r τ3 = 1.07
r (c)
4 r r
r
2 τ2 = 13.9 τ1 = 3.95
c3 c2 c1 c0
0
0 1 2 3 4 5 6
c
b T X T X(θ − θ)
(θ − θ) b
≤ χ 2 (np , α) (23)
σ2
b T X T X(θ − θ)
(θ − θ) b
2
≤ np F (np , nd − np , α) (24)
s
1 b T (y − X θ)
s2 = (y − X θ) b (25)
nd − np