L9b-1

Review: Analysis of Rate Data

Goal: determine reaction order, , and specific reaction rate constant, k
Data collection is done in the lab so we can simplify BMB, stoichiometry,
and fluid dynamic considerations
Want ideal conditions well-mixed (data is easiest to interpret)
Constant-volume batch reactor for homogeneous reactions: make
concentration vs time measurements during unsteady-state operation
Differential reactor for solid-fluid reactions: monitor product concentration
for different feed conditions during steady state operation
Method of Excess
Differential method
Integral method
Half-lives method
Initial rate method
Differential reactor
More complex kinetics
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-2

Review: Method of Half-lives

Half-life of a reaction (t1/2): time it takes
for the concentration of the reactant to A products dCA kC
A
drop to half of its initial value rA kC A dt

ln (t1/2)
1 1 1
t
k 1 C A 1
CA0
1

Slope = 1-
1
CA C A0 at t = t1 2
2

2 1 1 1
t1 2
k 1 CA0 1

ln CA0
Plot ln(t1/2) vs ln CA0. Get a straight 2 1 1
line with a slope of 1-

ln t1 2 ln
k 1
1 lnCA0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-3

Review: Method of Initial Rates

When the reaction is reversible, the method of initial
rates can be used to determine the reaction order and
the specific rate constant
Very little product is initially present, so rate of reverse
reaction is negligible
A series of experiments is carried out at different initial
concentrations
Initial rate of reaction is determined for each run
Initial rate can be found by differentiating the data and
extrapolating to zero time
By various plotting or numerical analysis techniques relating -rA0
to CA0, we can obtain the appropriate rate law:
rA0 kCA0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-4

Review: Differential Catalyst Bed

Conversion of reactants rA: rate of reaction per unit mass of catalyst
& change in reactant
concentration in the bed flow in - flow out + rate of gen = rate of accum.
is extremely small

L FA0 FAe rA W 0

FA0 FAe 0CA0 CAe

rA
W W
FA0 FAe
When constant flow rate, 0 = :
CA0 Cp
Fp 0 C A0 CAe 0Cp Product
rA concentration
W W
The reaction rate is determined by measuring
W product concentration, Cp
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-5

Review: Multiple Rxns & Selectivity

1) Parallel / competing rxns k1 k2
2) Series rxns A B C
k1 B Desired product
A
k1 k2
3) Complex rxns A+B C+D A+C E
k2 C
instantaneous rate selectivity, SD/U instantaneous yield, YD
rate of formation of D rD (at any point or time in reactor)
SD U rate of formation of D r
rate of formation of U rU YD D
rate of consumption of A rA
overall rate selectivity,S%D U
%
overall yield, Y
ND Final moles of desired product D
%
SD U FD at
%
NU Final moles of undesired product flow YD F F exit
A0 A
F Exit molar flow rate of desired product
S%D U D ND at
FU Exit molar flow rate of undesired product batch Y%
D tfinal
NA0 NA
Maximize selectivity / yield to maximize production of desired product
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Review: Maximizing SD/U for L9b-6

Parallel Rxns
ED EU

CA CB
AD 1 2 1 2 What reactor conditions and
SD U e RT configuration maximize selectivity?
AU
Specific rate of desired reaction kD increases:
a) If ED > EU b) If ED < EU
more rapidly with increasing T less rapidly with increasing T
Use lower temperature(not so low
Use higher temperature
that the reaction rate is tiny)
To favor production of the desired product
Now evaluate concentration:
a) 1 2 1 2 0 b) 1 2 1 2 0

Use large CA Use small CA

c) 1 2 1 2 0 d) 1 2 1 2 0
Use large CB Use small CB
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-7

Concentration Requirements &

Reactor
k
Selection D
D How do concentration requirements play
A+B into reactor selection?
kU
U CA00 CA0
CB00 CB0
CSTR:
PFR concentration is
PFR (or PBR): concentration is always at its
high at the inlet & progressively lowest value
drops to the outlet (that at outlet)
concentration
Semi-batch: concentration
Batch: CB0
of one reactant (A as
concentration is shown) is high at t=0 &
CA(t)
high at t=0 & progressively drops with
CB(t)
progressively drops increasing time, whereas
with increasing time CA concentration of B can be
kept low at all times
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
kD L9b-8
D High C favors desired High CA favors undesired
A+B A
product formation product formation
kU
U (keep CA low)
Batch reactor
PFR/PBR
Side streams feed low CA
High CB CA
When CA & CB are low (end time Semi-batch
favors or position), all rxns will be slow reactor slowly feed High CB
desired A to large amt of B
product PFR/PBR CA CA CA
formation High P for gas-phase rxn, do not CSTRs in
add inert gas (dilutes reactants) series
CA00 CA0
CB00 CB
CSTR
PFR/PBR w/ side streams feeding
High CB low CB CB
favors Semi-batch
undesired reactor, slowly High CA PFR/PBR
product feed B to large amount of A PFR/PBR w/ high
formation CB CB CB recycle
CSTRs in Dilute feed with inerts that are
(keep CB series
easily separated from product
low) B consumed
Slides courtesy of Prof before&leaving
M L Kraft, Chemical CSTR
Biomolecular Engr Low P if gas phaseUrbana-Champaign.
n Dept, University of Illinois,
L9b-9

Different Types of Selectivity

rate of formation of D rD
instantaneous rate selectivity, SD/U SD U
rate of formation of U rU
overall rate selectivity,S% DU

F Exit molar flow rate of desired product

S%D U D
FU Exit molar flow rate of undesired product

N Final moles of desired product

S%D U D
NU Final moles of undesired product

instantaneous yield, YD rate of formation of D r

YD D
(at any point or time in reactor) rate of consumption of A rA
%
overall yield, YD

% FD ND
batch Y%
Evaluated Evaluated
Y
flow D F F D
A0 A at outlet NA0 NA at tfinal
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-10

Series (Consecutive) Reactions

k1 k2
A D U Time is the key factor here!!!
(desired) (undesired)

Spacetime for a flow reactor Real time t for a batch reactor

To maximize the production of D, use:

Batch CSTRs in series

or PFR/PBR or
n

and carefully select the time (batch) or spacetime (flow)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-11

Concentrations in Series Reactions

k1 k2 -rA = k1CA
A B C rB,net = k1CA k2CB
How does CA depend on ?
dFA dC A
k1C A 0 k1C A C A C A0e k1
dV dV
How does CB depend on ?
dFB
dV
k1C A k 2CB 0
dCB
dV
k1 C A0e k1 k 2CB Substitute
V
0

dCB
d

k1 C A0ek1 k 2CB
dCB
d

k 2CB k1 CA0e k1
Use integrating
factor (reviewed

d CBek 2 k C e k 2 k1 CB k1CA0
ek1 ek 2

1 A0 k k
on Compass) d 2 1

CC CA0 CA CB
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-12

Reactions in Series: Cj & Yield

B CA CA0ek1
A C
ek1 ek 2
CB k1C A0
k k
2 1

CC CA0 CA CB
opt
The reactor V (for a given 0) and that maximizes CB occurs when dCB/dt=0
dCB k1CA0
d

k 2 k1

k1e k1
k 2 e k 2
0
1 k
opt ln 1
k1 k 2 k 2

V
so Vopt 0 opt
0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-13
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
kD 2000 E/R 300
A+C D desired
kU1 rD 800e T C A 0.5 CC rU 10e T CA CC
1
A+C U1 undesired
E
Need to maximize SD/U1

k T AeRT

ED EU
1
rD AD D U D U
SD U1 e T
CA 1
CC 1
rU1 AU1
2000 300 1700
Plug in
numbers:
SD U1
800
10
e T
CA0.51 CC11 SD U1 80e T C A 0.5

To maximize the production of the desired product, the temperature should be

a)As high as possible (without decomposing the reactant or product)
b)Neither very high or very low
E > EU, so use higher T
c)As low as possible (but not so low the rate = 0) D
d)Doesnt matter, T doesnt affect the selectivity
e)Not enough info to answer the question

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-14
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
kD 2000 300
A+C D desired
kU1 rD 800e T C A 0.5 CC rU
1
10e T C A CC
A+C U1 undesired
E
Need to maximize SD/U1 k T AeRT

ED EU
1
rD AD C D U1 C D U1
SD U1 e T
A C
rU1 AU1
2000 300 1700
Plug in
numbers:
SD U1
800
10
e T
CA0.51 CC11 SD U1 80e T C A 0.5

To maximize the production of the desired product, CA should be

a)As high as possible D < U1, so high CA favors undesired
b)Neither very high or very low product formation (keep CA low)
c)As low as possible
d)Doesnt matter, CA doesnt affect the selectivity
e)Not enough info to answer the question

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-15
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
kD 2000 300
A+C D desired
kU1 rD 800e T C A 0.5CC rU
1
10e T C A CC
A+C U1 undesired
Need to maximize SD/U1

ED EU
1
rD AD C D U1 C D U1
SD U1 e T
A C
rU1 AU1
2000 300 1700
Plug in
numbers:
SD U1
800
10
e T

CA 0.51 CC11 SD U 80e T C A 0.5
1
Since ED>EU1, kD increases faster than kU1 as the temperature increases
Operate at a high temperature to maximize CD with respect to CU1
D<U1, keep CA low to maximize CD with respect to CU1
rD and rU1 are 1st order in CC, so changing CC does not influence selectivity
HOWEVER, high CC will increase the reaction rate and offset the slow
reaction rate that is caused by low CA (thats a good thing)
What reactor should we use?
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-16
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
kD 2000 300
A+C D desired
kU1 rD 800e T C A 0.5CC rU 10e T C A CC
1
A+C U1 undesired
Need to maximize SD/U1
1700
SD U1 80e T C A 0.5
ED>EU1, operate at a high temperature to maximize CD with respect to CU1
D<U1, keep CA low to maximize CD with respect to CU1
rD and rU1 are 1st order in CC, so changing CC does not influence selectivity
HOWEVER, high CC will increase the reaction rate and offset the slow
reaction rate that is caused by low CA (thats a good thing)
What reactor should we use?

C PFR CA

Semi-batch reactor
A slowly feed A to large
PFR/PBR w/ side streams feeding low CA amount of C High CC

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-17
How does the selection of reactor/reactors scheme and conditions
change if D can react with C and form another undesired product?
kD kU1 kU2
A+C D desired A+C U1 undesired D+C U2 undesired
2000 300 8000
rD 800e T C A 0.5CC rU 10e T C A CC rU 106 e T CCCD
1 2
Need to maximize SD/U1 and SD/U2
ED>EU1, operate at a high T
1700 D<U1, keep CA low
0.5
SD U1 80e T C A High CC increases rxn rate &
offsets slow rxn from low CA
2000
6000
rD 800e T CA 0.5CC 4 T C 0.5C 1
SD U2 8000
SD U2 8 10 e A D
rU2
106 e T CCCD
Since ED<EU21, kD increases slower than kU2 as T increases operate at low
T to maximize CD Conflicts with maximizing SD/U1!
D>U2, keep CA high to maximize CD Conflicts with maximizing SD/U1!
rD, rU1 & rU2 are all 1st order in CC, so changing CC does not influence
selectivity, but high CC will offset the rate decrease due to low CA
Low CD reduces the production of U2 Conflicts with producing the product D!!!
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-18
kD kU1 kU2
A+C D desired A+C U1 undesired D+C U2 undesired
1700 6000
SD U1 80e T C A 0.5 Maximize SD/U1 & SD/U2 SD U2 8 104 e T C A 0.5CD1
ED>EU1, operate at a high T ED<EU2, operate at low T
D<U1, keep CA low D>U2, keep CA high
Want to maximize CD Low CD reduces production of U2
High CC increases rxn rate & offsets slow rate caused by low CA
Consider relative magnitude of SD/U1 and DD/U2 as a function of position in PFR
PFR w/ side streams feeding low CA
C PFR, high T PFR 2, low T

A
High T, CC is initially high, CA is low At some distance down the reactor,
high SD/U1 significant amounts of D have formed
Initially CD=0 rU2=0. Both gradually SD/U2 becomes significant with respect
increase down reactor to SD/U1
Initially high SD/U2 (because CD is low), At this point, want low T, high CA &
but SD/U2 gradually decreases down low CC
reactor
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-19
If a CSTR were used with CA = 1 mol/L and CD= 1 mol/L, at what
temperature should the reactor be operated?
kD kU1 kU2
A+C D desired A+C U1 undesired D+C U2 undesired
2000 300 8000
rD 800e T C A 0.5CC rU 10e T C A CC rU 106 e T CCCD
1 2
Need to maximize SD/(U1+U2)
2000
800e T C A 0.5CC CA=1
rD
SD U U 300 CD=1
1 2 rU1 rU2 8000

10e T C C 106 e T C C
A C C D
2000
800 0.5 2000
e T 1 80e T
S 10
D 300
S D
8000 300 8000
U1U2 10 T 106 U1U2
e 1 e T 1 e T 105 e T
10 10

Plot SD/(U1+U2) vs temperature to find the temperature that maximizes SD/(U1+U2)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-20
If a CSTR were used with CA = 1 mol/L and CD= 1 mol/L, at what
temperature should the reactor be operated?
k k k
A+C D D desired A+C U1 U1 undesired D+C U2 U2 undesired
2000 300 8000
rD 800e T C A 0.5CC rU1 10e T C A CC rU2 106 e T CCCD

Need to maximize SD/(U1+U2) 600K

2000
80e T
S D
300 8000
U1U2
e T 105 e T
SD/(U1+U2)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-21
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
kB mol kC
A B rB kB 2 A C rC k CC A k C 1 min1
L min
What is the expression for the yield of B for a CSTR?
% FB % CB0 % CB
YB Y Y
FA0 FA (overall yield)
B B
C A00 CA0 CA0 CA

We know CA0 and CA when XA=0.9. How do we get CB?

In - Out + Gen. = Accum.
dNB C
FB0 FB rB V FB rB V 0 rB B 0
dt V
0 0
CB mol CB mol
rB rB 2 2 CB
L min L min
Use the mole balance on A to find (at 90% conversion)
In - Out + Gen. = Accum.
dNA C A00 CA0 rA V
FA0 FA rA V
dt 0
V C CA
C A0 C A rA CA0 CA rA A0
0 rA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-22
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
kB mol kC
A B Br k B 2 A C rC k CC A k C 1 min1
L min
CB mol CA0 CA rA rB rC
Y%
B 2 CB What is rA?
CA0 CA L min rA
mol 1 Plug -rA back into
rA kB k CCA rA 2 CA
L min min expression for
CA0 CA C A0 CA CA0 = 4 mol/L, and at

rA mol 1 XA=0.9, CA= 0.4 mol/L
2 CA
L min min
mol mol
4 0.4
L L 1.5 min Residence time for XA = 0.9
mol 1 mol
2 0.4
L min min L
mol
rB 2 1.5min
Y%
B Y% L min
CA 0 CA B Y%
B 0.83
mol mol
4 0.4
L L
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-23
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
kB mol kC 1
A B B r k B 2 A C rC k C C A k C 1 min
L min
mol 1
rA kB k CCA rA 2 CA
L min min
What is the expression for the yield of B for a PFR?
% FB (overall yield) % CB0 % CB
YB YB Y B
FA0 FA C A00 CA0 CA0 CA
Use the mass balance to get CB
dFB dCB0 dCB dCB mol
rB rB rB 2
dV dV d d L min
CB
mol mol mol
dCB 2

d CB CB0 2 0 CB 2
CB0 L min 0 L min L min
0
Use the mole balance on A to find (at 90% conversion)
dFA dC A0 dC A dCA mol 1
rA rA rA 2 C A
dV dV d d L min min
dCA mol 1
CA dCA 1
2 CA d
d L min CA0 2mol L C A min 0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-24
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
kB mol kC
A B rB kB 2 A C rC k CC A k C 1 min1
L min
mol 1
rA kB k CCA rA 2 C
L min min A
CB mol
Y%
B C 2
CA0 CA B Use mole balance on A to find (at XA = 0.9)
L min
mol
2 C A0
CA dCA 1 L 1 0
d ln
CA0 2 mol
C
min 0

mol
2 C
min
A A
L L
mol mol
2 4
CA0 = 4 mol/L ln L L 1
0.92 min
CA = 0.4 mol/L mo l mol min
2 0. 4
L L
mol Yield was better
C r 2 0.92m in
% B B % L min % in the CSTR, but
YB YB YB 0.51
CA0 CA C A0 CA mol mol the residence
4 0.4 time was longer
L L
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.