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Youn-Woo Lee
School of Chemical and Biological Engineering
Seoul National University
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea ywlee@snu.ac.kr htp:/sfpl.snu.ac.kr
第5章
Collection and Analysis of Rate Data
化學反應裝置設計
★ Describe how the methods of half lives, and of initial rate, are
used to analyze rate data.
t CA
0 50.0 Measuring concentration
50 38.0 as a function of time
100 30.6
.. ..
Differential,
Data
integral
analysis
or nonlinear regression method
Determining and k
in -rA = kCA
Irreversible reaction
-Determine and k
by either nonlinear regression or by numerically
differentiating concentration versus time data
For example
-for decomposition reaction (only one reactant)
(5-3) (5-4)
Once and are determined, kA can be calculated from the measurement of -rA
at known concentration of A and B
r
kA A
dm / mol
3 1
CACB s (5-5)
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5.2.1 Differential Method of Analysis
dC A
k AC A (5-6)
dt
dC A
ln ln k A ln C A (5-7)
dt
dC A
ln ln k A ln C A
dt
ln ln
P
P kA=
slope= ( Ap )
C
ln ln
C CA
A p
dC A
To obtain the derivative –dCA/dt used in this plot,
dt
we must differentiate the concentration-time data
either numerically and graphically. These methods are:
★ Graphical differentiation
★ Numerical differentiation formulas
★ Differentiation of a polynomial fit to the data
Time (min) t0 t1 t2 t3 t4 t5
1. Tabulate the (ti, Ci) Concentration (mol/dm3) C0 C1 C2 C3 C4 C5
0 1 2 3 4 5
Time (min) t0 t1 t2 t3 t4 t5
Concentration (mol/dm3) CA0 CA1 CA2 CA3 CA4 CA5
★ Polynomial Fit
Time (min) t0 t1 t2 t3 t4 t5
Concentration (mol/dm3) CA0 CA1 CA2 CA3 CA4 CA5
t5
Care must be taken in choosing the order of the polynomial. If the order is too
low, the polynomial fit will not capture the trends in the data. If too large an order
is chosen, the fitted curve can have peaks and valleys as it goes through most all
of the data points, thereby producing significant errors when the
derivatives, dCA/dt, are generated at the various points. Seoul National University
Finding the Rate Law Parameter
The reaction of triphenyl methyl chloride (trityl) (A) and methanol (B) was
carried out in a solution of benzene and pyridine at 25oC. Pyridine reacts with
HCl that then precipitates as pyridine hydrochloride thereby making the reaction
irreversible. The concentration-time data was obtained in a batch reactor. The
initial concentration of methanol was 0.5 mol/dm3.
50
CA x 10 (mol/dm )
3
45
40
35
3
30
25
20
15
0 50 100 150 200 250 300
t (min)
Solution
Part (1) Determine the reaction order with respect to trityl (A)
Step 2 Process your data in terms of the measured variable, which is this case is CA.
CB C B0 (E5-1.2)
r k C C kC (E5-1.3)
A A B0 A A
dN A
Mole Balance rAV (E5-1.4)
dt
Rate law r k C (E5-1.3)
A A
V V0
Stoichiometry: Liquid NA
CA
V0
dC A
Combine K CA (E5-1.5)
dt
Example 5-1: Determining the Rate Law
ln A ln k ln C
dC (E5-1.6)
dt
A
ln
dCA
The slope of plot of versus lnC A will yield the reaction order
dt
with respective to triphenyl methyl chloride (A).
dC A
Step 5 Find as a function of CA from concentration-time data.
dt
dC A
We will find by each of the three methods just discussed, (1) the graphical
dt
(2) finite difference, and (3) polynomial methods.
dCA
3.0 3.0
dt 0
CA
2.4
t 1
dCA 2.0
dt 1 1.86
CA
1.48
dCA t 2
dt 2 1.2 C A
1.0 1.00
dCA t 3 CA
dt 40.8 0.68 t 4
0.5 CA
0.47 0.54 t 5
0.42
0.0
0 50 100 150 200 250 300
dt t 0 2t 2 (50 )
dC C C [30 .6 50 ] 10 3
t 50 A A2 A0
1 .94 10 4
dt t 1 2t 2(50 )
dC A C C [ 25 .6 38 ] 10 3
t 100 A3 A1
1 .24 10 4
dt t 2 2t 2(50 )
dC C C [ 22 .2 30 .6 ] 10 3
t 150 A A4 A2
0 .84 10 4
dt t 3 2t 2 (50 )
dC C C [19 .5 25 .6 ] 10 3
t 200 A A5 A3
0 .61 10 4
dt t 4 2t 2 (50 )
dC C C [17 .4 22 .2 ] 10 3
t 250 A A6 A4
0 .48 10 4
dt t 5 2t 2(50 )
dC C 4 C A 5 3C [ 22 .2 4 (19 .5 ) 3(17 .4 )] 10 3
t 300 A A4 A6
0 .36 10 4
dt t 6 2t 2 (50 )
4 6 2 9 3 12 4
C A 0.04999 2.97810 t 1.34310 t 3.48510 t 3.697 10 t
dC A
10 3 2.978 0.002686 t 1.045 10 5 t 2 1.479 10 8 t 3
dt
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Example 5-1: Determining the Rate Law
Step 5A.1c Polynomial method
4 6 2
C A 0.04999 2.978 10 t 1.34310 t 3.485109 t 3 3.697 1012 t 4
dC A
0.5104 mol/dm3 min
dt p
then
dC A
dt p 0.5104 mol/dm3 min dm 3
k 0.125
2
C Ap
20 10 3 mol/dm 3
2
mol min
1.99
dC A
104
dt 1.00 k 0.13 dm /mol
3
min
mol
dm3 min 0.5
Graphical
Finite Regression again
Polynomial
0.10
10 20 100 2
mol
C A 10 4 3
dm k 0.122 dm /mol
3
min
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Graphical
Finite
Polynomial
Example 5-1: Determining the Rate Law
Part (2) The reaction was said to be first order wrt methanol, =1,
k kC C k
B0 B0
rA 0.244(dm 3 /mol) 2 / min C A2 C B
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Integral Method
★ The integral method uses a trial-and-error procedure to find rxn order:
We guess the reaction order and integrate the differential equation used to
model the batch system. If the order we assume is correct, the appropriate
plot of the concentration-time data should be linear.
★ The integral method is used most often when the reaction order is
known and it is desired to evaluate the specific reaction rate constants
at different temperatures to determine the activation energy.
★ Finally we should also use the formula to plot reaction rate data in
terms of concentration vs. time for 0, 1st, and 2nd order reactions.
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zero order first order second order
dCA dC A
dC A kC A kC A
2
k dt dt
dt
@ t 0, C A C A0 @ t 0, C A C A0
@ t 0, C A C A0
CA 1 1
C A C A0 kt ln kt kt
C A0 C A C A0
C A0
slope = -k
CA C 1
ln A slope = k slope = k
CA0 CA
t t t
The rxns are zero, first, and second order respectively since the plots are linear.
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second order
dC A
kC A
2
dt
1
@ t 0, C A C A0
CA
non linear
1 1
kt
C A C A0
t
Use the integral method to confirm that the reaction is second order with respect
to trityl(A) as described in example 5-1 and to calculate the specific reaction rate k'.
Trityl(A) + Methanol (B) Products
dC A
kC A kC
2
A
dt
1 1
k t
C A C A0
Time (min) 0 50 100 150 200 250 300
CA (mol/dm3) 0.05 0.038 0.0306 0.0256 0.0222 0.0195 0.0174
1/CA (dm3/mol) 20 26.3 32.7 39.1 45 51.3 57.5
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Example 5-2
1
second order 0.12t 20.12
CA
60
Experiments
Regression
50
1/CA (dm /mol)
3
40
1 1
30
k t
C A C A0
20
0 50 100 150 200 250 300 350
t (min)
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Example 5-2
Note that differential method gives r A 0.244(dm3/mol) 2/ min C C
2
A B
a0 20.1142857143 18
24
30
22.3617142857
23.1108571429
23.86
174
180
186
41.8394285714
42.5885714286
43.3377142857
36 24.6091428571 192 44.0868571429
k’ 0.1248571429 42
48
25.3582857143
26.1074285714
198
204
44.836
45.5851428571
54 26.8565714286 210 46.3342857143
r² 0.999903135 60
66
27.6057142857
28.3548571429
216
222
47.0834285714
47.8325714286
72 29.104 228 48.5817142857
78 29.8531428571 234 49.3308571429
84 30.6022857143 240 50.08
90 31.3514285714 246 50.8291428571
96 32.1005714286 252 51.5782857143
102 32.8497142857 258 52.3274285714
108 33.5988571429 264 53.0765714286
114 34.348 270 53.8257142857
120 35.0971428571 276 54.5748571429
126 35.8462857143 282 55.324
k=0.25 dm3/mol/min 132 36.5954285714 288 56.0731428571
138 37.3445714286 294 56.8222857143
144 38.0937142857 300 57.5714285714
150 38.8428571429
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Example 5-1: Determining the Rate Law
50
1.0
CA x 103 (mol/dm3)
45
0.8
40
ln (CA/CA0)
35 0.6
30
0.4
25
0.2
20
15 0.0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
t (min) t (min)
s 2 N
(r r ) 2
2 im ic (5-34)
N K i1 N K
N = number of runs
K = number of parameters to be determined
rim = measured reaction rate for run i (i.e., -rAim)
ric = calculated reaction rate for run i (i.e., -rAic)
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Nonlinear Regression
A Product
for which we want to learn the reaction order, , and the specific reaction rate, k,
r kCA
2 2 57
2.0 2 13.25
k 5.0 dm3/mol s 2 7.3
2 1.85
5
2
f (k, )
min
2
0.045
2
C 1
A0
C 1
A (1 )kt
A0 (1 )kt
C A C 1
1/(1 )
(5-18)
We want the value of and k that will make s2 a minimum.
C Ami C
N N
s
2
(C Ami CAci ) 2 1
A0 (1 )kti
1/(1 )
2 (5-19)
i1 i1
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Nonlinear Regression (Nonlinear Least-SquaresAnalysis)
We shall use the reaction and data in Ex. 5-1 to illustrate how to use regression
to find and k’
(C6H5)3CCl (A) + CH3OH (B) (C6H5)3COCH3 (C) + HCl (D)
dC A
kC A
dt
Integrating with the initial condition when t=0 and CA=CA0 for ≠1.0
(1 ) )
1 C A0 C (1
t A
k (1 )
Substituting for the initial concentration CA0=0.05 mol/dm3
(1 )
1 (0.05)(1 )
C
t
A
k (1 )
We now first assume a value of and k and then calculate t for the
concentrations of A given in Table E5-1.1 (pp 261). We will then calculate the sum
of the squares of the difference between the measured time, tm and the calculated
times (i.e., s2). For N measurements,
N N
1
C C
1 2
mi ci tmi
t1
A0
k(1 )
A
t1
1 1 1 1 1
t c1 2 2 400
2k C A C A0 10 C A
2
We now make the calculations for each measurement of concentration and fill in
column 3 and 4 of Table E5-3.1. For example, when CA=0.038 mol/dm3 then
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Example 5-3 Use of Regression to find the Rate Law Parameter
1 1 1 1 1
t c1 2 2 400 29.2 min
2k C A C A0 10 (0.038) 2
Which is shown in Table E5-3.1 on line 2 for guess 1. We next calculate the squares
of difference (tm1-tc1)2=(50-29.2)2=433. We continue in this manner for points 2, 3, and
4 to calculate the sum s2=2916.
After calculating s2 for = 3 and k = 5, we make a second guess for and k’. For
our second guess we choose = 2 and k = 5; Equation (E5-3.2) becomes
1 1 1 1 1 20
tc (E5-3.2)
k C A C A0 5 C A
We now proceed with our second guess to find the sum of (tm1-tc1)2 to be s2=49,895,
which is far worse than our first guess. So we continue to make more guesses of
and k and find s2. Let’s stop and take a look at tc for guesses 3 and 4S.eoulNational University
Example 5-3 Use of Regression to find the Rate Law Parameter
0 50 0 0 0 0 0 0 0 0
1
50 38 29.2 433 1.26 2,375 31.6 339 63.2 174
2
100 30.6 66.7 1,109 2.5 9,499 63.4 1,340 126.8 718
3
200 22.2 163 1,375 5.0 38,622 125.2 5,591 250 2,540
4
s2 = 2,916 s2 = 49,895 s2 = 7,270 s2 = 3,432
2.04
k 0.147 dm3/mol min
Regression again
2.0
k 0.125 dm3/mol min
rA 0.25(dm3 /mol) 2 / min C A2 C B
In these cases, the method of initial rates could be used to determine the
reaction order and the specific rate constant. Here, a series of
experiments is carried out at different initial concentrations, CA0, and the
initial rate of reaction, -rA0, is determined for each run.
The initial rate of reaction –rA0 can be found by differentiating the data
and extrapolating to zero time.
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5.3 Method of Initial Rates
r kC
A0 A0
the slope of the plot of ln(-rA0) versus lnCA0 is the reaction order
Solution
k ( 1) C 1
A0
2 1 1
ln t1/ 2 ln (1 ) ln C A0
ln C A0 k( 1)
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Differential Reactors
A P
FA0 FAe
L Inert filling
catalyst
rate of reaction
e
CA0 FP [FA0 ] [FAe ] (mass of cat.) 0
mass of cat.
C
P
F F (r ' )(W ) 0
W A0 Ae A
FA0 FAe
r '
W
A P A
0 C A0 C A
r '
(5-27)
A
W e
Reactor Design Equation
FA0 X FP
r ' (5-28)
W A
W
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Differential Reactors
For constant volumetric flow known
Measuring
Can be determined the product
C A0 C Ae (CA0 CAe ) 0CP
r
' 0 0 concentration
A
W W W
known
- using very little catalyst and large volumetric flow rates (CA0 C Ae ) ~ 0
r ' r ' (C )
A A Ab
C A0 C Ae
- the arithmetic mean of the inlet and outlet concentration: C Ab
2
- very little reaction takes place within bed: C Ab ~ C A0
r ' r ' (C )
A A A0
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Example 5-5 Differential Reactors
The synthesis of CH4 from CO and H2 using a nickel catalyst was carried out at 500oF
in a differential reactor where the effluent concentration of CH4 was measured.
3H 2 CO CH 4 2H 2O
a. Relate the rate of reaction to the exit methane concentration.
b. The reaction rate law is assumed to be the product of a function of the partial
pressure of CO and a function of the partial pressure of H2:
Determine the reaction order w.r.t. CO, using the data in Table E5-5.1.
Assume that the functional dependence of rCH on PCO is of the form
4
4 ~ PCO
rCH (E5-5.2)
4
rCH
kP g(P ) kP
(E5-5.4)
CO H2 CO
4 0.0056 PCO
rCH 1.22
0.01
0.001
0.1 1 10
Pressure of CO (atm)
Had we include more points, we would have found the reaction rate is
essentially first order with =1, that is,
=1.22 → 1
4 0.0056 PCO
rCH 1.22
rCH 4 kPCO (E5-5.5)
rCH k PCOf(PH )
4 2
From Table E5-5.2, it appears that the dependence of r’CH4 on PH2 cannot be
represented by a power law. The reaction rate first increases with increasing
partial pressure of hydrogen, and subsequently decreases with increasing partial
pressure of hydrogen. That is, there appears to be a concentration of hydrogen at
which the rate is maximum.
Run PCO (atm) PH2 (atm) CCH4 (mol/dm3) r´CH4 (mol CH4/cat·min)
1 1.0 1.0 1.73x10-4 5.2x10-3
2 1.8 1.0 4.40x10-4 13.2x10-3
3 4.08 1.0 10.0x10-4 30.0x10-3
4 1.0 0.1 1.65x10-4 4.95x10-3
5 1.0 0.5 2.47x10-4 7.42x10-3
6 1.0 4.0 1.75x10-4 5.25x10-3
@ low PH2
4 ~ PHβ21
rCH
PHβ21
4 ~
rCH 2 1
1 bP β2
H2
aPCO PHβ 1
rCH 2
4
1 bPHβ 2
2 Polymath
Regression
(E5-5.11)
0.025PCO PH0.61
4
rCH 2
1 2.49PH2
Hydrogen undergo
(E5-5.12) dissociate adsorption
on the catalyst surface
→ Dependence of H2 to the ½ power
Polymath
Regression
0.018PCO PH0.52
again 4
rCH
1 1.49PH2
1 12 , 2 1
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Example 5-5 Differential Reactors
This plot should be a straight line with an intercept of 1/a and a slope b/a.
400
0.018P P0.5
rCH 4 CO H2
300 1 1.49PH 2
PCO PH0.52
rCH
4 200
Rate law is
100
indeed
consistent with
the rate law
0 data
0 1 2 3 4
PH (atm) Seoul National University
2
5.7 Evaluation of Laboratory Reactor
catalyst slurry
CSTR and recirculating transport reactor appear to be the best choice, because they are
satisfactory in every category except for construction. However, if the catalyst under
study does not decay, the stirred batch and contained solid reactors appear to be best
choices. If the system is not limited by internal diffusion in the catalyst pellet, larger
pellets could be used, and the stirred-contained solids is the best choice. If the catalyst
is nondecaying and heat effects are negligible, the fixed-bed (integral) reactor would be
the top choice, owing to its ease of construction and operation. However, in practice,
usually more than one reactor type is used in determining the reaction rate law
parameters. Seoul National University