Lecture 11
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Transcript of Lecture 11
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Chemical Reaction Engineering (CRE) is the field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in which they take place.
Lecture 11
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Today’s lectureDetermining the Rate Law from
Experimental DataIntegral MethodDifferential (Graphical) MethodNonlinear Least Regression
Multiple ReactionsThe Four TypesWhat’s New to Our AlgorithmReactions in Series
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Integral MethodConsider the following reaction that occurs in a constant volume Batch Reactor: (We will withdraw samples and record the concentration of A as a function of time.)A Products
dNAdt
rAVMole Balance:
rA kCARate Law:
V V0Stochiometry:
dCAdt
kCACombine:
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Finally we should also use the formula to plot reaction rate data in terms of conversion vs. time for 0, 1st and 2nd order reactions.
Derivation Equations used to Plot 0, 1st and 2nd order reactions.These types of plots are usually used to determine the values k for runs at various temperatures and then used to determine the activation energy.Zero order First Order Second
Order
dCAdt
rA k
at t 0, CA CA 0
CA CA 0 kt
dCAdt
rA kCA
at t 0, CA CA 0
lnCA 0
CA
kt
dCAdt
rA kCA2
at t 0, CA CA 0
1CA
1CA 0
kt4
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Guess and check for α = 0, 1, 2 and check against experimental plot
ktCC
ktCCktCr
AAA
AAA
0
00
11 ln
2 1 0
t
CA
t
ln(CA0/CA)
t
1/CA
Finding the Rate law (Integral Method)
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Differential Method
AA Clnkln
dtdCln
AA kC
dtdCTaking the natural log of
dCAdt
vs CAThe reaction order can be found from a ln-ln plot of:
dtdCA
ACAPC
P
A
dtdC
Slope = α
ln
ln
Ap
p
A
C
dtdC
k
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Methods for finding the slope of log-log and semi-log graph papers may be found at
http://www.physics.uoguelph.ca/tutorials/GLP/.
However, we are usually given concentration as a function of time from batch reactor experiments:time (s) 0 t1 t2 t3
concentration (moles/dm3)
CA0 CA1 CA2 CA3
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Three Ways to determine (-dCA/dt) from Concentration-Time Data Graphical differentiationNumerical differentiation formulasDifferentiation of a polynomial fit to the data1. Graphical
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CAt
t
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The method accentuates measurement error!
1t
A
dtdC
CAt
0
A
dtdC
2t
A
dtdC
0 1t 2t t
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Example - Finding Rate Lawt(min) 0 1 2 3
CA(mol/L) 1 0.7 0.5 0.35
0.3 0.2 0.15tCA
tCA
.1.2.3
t1 2 3
Areas equal for both sides of the histogram
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Example - Finding Rate LawFind the f(t) of using equal area differentiation t
CA
CA 1 0.7 0.5 0.35-dCA/dt 0.35 0.25 0.175 0.12Plot –dCA/dt as a function of CA
Ap
p
A
C
dtdC
k
ln
CA
Slope = α
dCA/dt
ln11
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Non-Linear Least-Square Analysis
2 rmi rci 2
N Ki1
n
That is we want to be a minimum.
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We want to find the parameter values (α, k, E) for which the sum of the squares of the differences, the measured rate (rm), and the calculated rate (rc) is a minimum.
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Non-Linear Least-Square AnalysisFor concentration-time data, we can integrate the mole balance equation for to obtain
rA kCA
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dCAdt
kCA
t 0
CA CA 0
CA CA 01 1 kt 1
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Non-Linear Least-Square Analysis
s2 CAmi CAci 2
i1
N
CAmi CA 01 1 kti 1 1 2
i1
N
We find the values of alpha and k which minimize s2
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Cmeas 1 0.7 0.5 0.35CCalc 1 0.5 0.3
30.25
(Cc-Cm) 0 -0.2 -0.17
-0.10
(Cc-Cm)2 0 0.04
0.029
0.01 0.07for α= 2, k = 1 → S2 = 0.07for α = 2, k = 2 → S2 = 0.27etc. until S2 is a minimum15
Regression MethodGuess values forα and k and solve for measured data points then sum squared differences:
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Residuals
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End of Lecture 11
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