Chemical Kinetics and Reactor Design Course Review

J. B. Rawlings
Department of Chemical and Biological Engineering
University of Wisconsin
May 25, 2006

Stoichiometry

j : chemical potential for species j.



-*- CO2 + H2
H2 O + CO )
-*H2 O + H )

G
i


=
T ,P

Ki =
A1 = H, A2 = H2 , A3 = OH, A4 = H2 O, A5 = CO, A6 = CO2 .
ij Aj = 0,

ij j = 0,

i = 1, . . . , nr

j=1

j = Gj + RT ln aj ,

H2 + OH

-*- CO2 + H
OH + CO )

ns
X

ns
X

ns
Y

ij

aj

aj = fj /fj

Gi = RT ln Ki

j=1

Standard state: pure species j at 1 atm and system temperature.

i = 1, . . . , nr

j=1

Phase Equilibrium
ij > 0, for Aj product; ij < 0, for Aj reactant.

A = 0,

= 1
1

1
1
0

0
1
1

1
1
0

1
0
1

fj = fj ,
1

0
1

nr
X

ij ri ,

Temperature Dependence of K
Hi
ln Ki
(Vant Hoff Equation)
=
T
RT 2




Hi 1
Ki2
1
ln
=

(assumption?)
Ki1
R
T2
T1

j = 1, . . . , ns

i=1
T

R= r
Extent of reaction: dnj =

Pnr

i=1

ij di ,

How does raising temperature affect the equilibrium

extent for exothermic and endothermic reactions?

j = 1, . . . , ns .

Thermodynamics

Arrhenius expression for k: k(T ) = k0 eEa /RT , Ea is the activation energy, always positive. How does raising temperature affect reaction rate? What is f (cj s) for a sequence of
elementar y steps. What is the difference between a mechanism and an overall stoichiometry. Quasi-steady-state assumption, equilibrium assumption and rate limiting step.

Chemical Equilibrium
ns
X

Reaction-Rate Expressions
r = k(T )f (cj s)

At equilibrium, for a given T and P , the Gibbs free energy

is a minimum.

dG = SdT + V dP +

all phases and

Know how to evaluate fugacities for ideal gases, ideal

solutions, and Raoult and Henry law approximations.

ri : reaction rate for reaction i.

Rj : production rate for species j.
Rj =

j = 1, . . . , ns ,

j dnj

j=1

BATCH
constant volume
SEMI-BATCH
CSTR
constant volume

d(cj VR )
= Rj VR
dt
dcj
= Rj
dt

d(cj VR )
= Qf cjf Qcj + Rj VR
dt
dcj
1
=
(cjf cj ) + Rj
dt

r extinction point

420

0.7

400

0.6
x 0.5

T (K)

380
360

0.4

340

0.3

320

0.2

r ignition point

0.1

r ignition point

300

280
0

10

15

20

25

30

35

40

45

10

15

(min)

20

25

30

35

40

45

(min)

Figure 2: CSTR steady-state multiplicity, stable and unstable steady states, ignition, extinction, hysteresis.

(cj Q)
cj
=
+ Rj
t
V

PFR

constant density

440

r extinction point

0.8

cj = cjf + Rj

steady state

steady-state

460

1
0.9

d(cj VR )
= Qf cjf + Rj VR
dt

400

d(cj Q)
= Rj
dV
dcj
= Rj
d

380
x(t)
360
x 0.5

340 T (K)
320
300

T (t)

Langmuir Isotherms (chemisorption)

0
0

-*- A X
A+X )

cA =

100

200

300

400

500

280
600

time (min)

KA cA c m
1 + KA cA

Figure 3: CSTR oscillations.

Hougen-Watson rate expressions Deciding which mechanism best explains rate data.

Material and Energy Balances

BATCH

CSTR

P dT =
VR C
dt

P dT =
VR C
dt

V
m1

m0
cj0

(steady state)

Z
V

cj dV = Q0 cj0 Q1 cj1 +

cjf Qf (H jf H j )

PFR

Figure 1: Reactor volume element.

d
dt

HRi ri VR + Q

E1
cj1

E0

HRi ri VR + Q

Rj dV ,

P
Q C

X
dT

= HRi ri + q
dV
i

Table 1: Summary of Material and Energy Balances for Several Ideal Reactors.

j = 1, . . . , ns

dU
+W
0 m1 H
1 + Q
s + Wb
= m0 H
dt

cj
cjs

= 0.1

1
0.8

D
c
T
cj

= 0.5

0.6
0.4

Te
cej

= 1.0

0.2
= 2.0
0

0.5

1.5

2.5

Figure 4: Expanded views of a fixed-bed reactor.

n=1
n=2
n=5
n = 10

Fixed-Bed Catalytic Reactors

Steps in a Catalytic Reactor

1. convection of reactant in the bulk fluid

sphere(1)
cylinder(2)
slab(3)

0.1

0.01

0.1
0.1

10

2. mass transfer from bulk fluid to catalyst

0.001
0.01

0.1

3. diffusion of reactant in the pores (molecular and Knudsen diffusion)

10

100

Figure 5: Effectiveness Factor Versus Thiele Modulus: Effect

of Geometry and Reaction Order.

4. adsorption of reactant on the active sites

5. reaction of adsorbed reactants to adsorbed products
(surface reaction)

dNj
= Rj
dV
X
p dT = HRi ri + 2 U o (Ta T )
Q C
dV
R
i
"
#
(1 B )f
dP
7 Q
(1 B ) Q
150
+
=
dV
Dp
4 Ac
Dp B3 A2c

6. desorption of adsorbed products

7. diffusion out of pores
8. mass transfer from catalyst to bulk fluid
9. convection of product in the bulk fluid
Simultaneous Reaction and Diffusion

e jp
Rj = (1 B )R
X
HRi ri = (1 B ) HRi reip

cj
= Dj 2 cj + Rj
t

B = 1 b /p ,

Q=

Nj /c(P , T )

1st order reaction, spherical pellet, steady state:

1
c
r2
r 2 r
r
c = 1,
c
= 0,
r


Biot number: B = km a/DA

= RAp /RAb

2 c = 0
r

3 sinh r
Solution: c(r ) =
r sinh 3
!
n1 1/2
n + 1 kcAs
Thiele modulus: = a
2
DA
Effectiveness factor:
actual rate in pellet
=
rate without diffusional limitations

Vp
a=
Sp

Sphere

1
=

Cylinder

1 I1 (2)
I0 (2)

(2)

Slab

tanh

(3)

1
1

tanh 3
3


(1)

Table 2: Effectiveness factor versus Thiele modulus for the

sphere, semi-infinite cylinder, and semi-infinite slab.
3

x T Ax = b
1

Av i = i v i
101

B1 = 0.01
B2 = 100

102

x2
q

3
10

b
2 v 2

104

b
1 v 1

105
p

p
B1
106
102

B2

q
101

101

102

103

104

x1

22
bA

q
11
bA

Figure 6: Effectiveness factor versus Thiele modulus for different values of the Biot number; first-order reaction in a
spherical pellet.

ii =
Figure 7: The geometry of quadratic form x T Ax = b. A
1
(i, i) element of A .

Mixing in Chemical Reactors

b N(, P),

Residence-time distribution

Confidence interval. -level confidence region for estimatprobability that a feed molecule spends time ing np parameters is given
to + d in the reactor
b T X T X( )
b
probability that a feed molecule spends time
( )
2 (np , )
2
zero to in the reactor

p()d,
P (),

Zt
ce (t) =

cf (t 0 )p(t t 0 )dt 0 ,

b T X T X( )
b
( )
np F (np , nd np , )
2
s
1
b T (y X )
b
s2 =
(y X )
nd np

cf (t) = 0, t 0

Step response, impulse response for CSTR, PFR, n CSTRs,

PFR with dispersion.

Parameter Estimation

1
exp (x m)T P 1 (x m)
2


(2 )np /2 |P|1/2

Least squares. Let y be measured as a function of x

yi = mxi + b,
y = X + e,

Notes

Gas constant: R = 82.06 cm3 atm/molK; R = 1.987

cal/molK

Probability review. Normal distribution, mean, variance.

!
1
1 (x m)2
p(x) =
exp
2
2
2 2
p(x) =

P = 2 (X T X)1

i = 1, . . . n
e N(0, 2 I)

The best estimate of in a least squares sense is given by

b = (X T X)1 X T y