Chapter 5

Collection and Analysis of Rate Data

 Flowchart for Experimental Projects

2
 Finding the Rate Law

 Batch Reactor:

➢ Used for homogeneous reactions

➢ Data: Cj, P, and/or V = f(t)

 Differential Reactor:

➢ Used for solid-fluid reactions

➢ Product concentration for different feed conditions (@ s.s.)

3
 Differential Method
 Applicable when

➢ the reaction is irreversible

➢ rate = f(conc. of only one reactant) (or use method of excess, p. 256)
➢ constant volume

 Consider the reaction: A → Products

dN A
Mole Balances: = rAV
dt
Rate Laws: − rA = k AC A
Stoichiometry:  V = V0
Combine: dC A
4
− = k AC A
dt
  dC A 
Taking the natural log of −
 dt = k C
A A

 dC 
ln  − A  = ln k A +  ln C A
 dt 
 dCA 
The reaction order can be found from a ln-ln plot of:  −  vs CA
 dt 
dC A ln
−
dt

dCA  dC A 
−
Slope = α − 
 dt  p
dt P

kA = 
C Ap
ln
C AP CA
Choose a point, p, and find the concentration and derivative at that point to determine k.
5
• However, we are usually given concentration as a function of time
from batch reactor experiments

time (s) 0 t1 t2 t3

concentration (mol/dm3) CAo CA1 CA2 CA3

• Three ways to determine (-dCA/dt) from Concentration-Time Data:

– Graphical Method (Appendix A2)

– Numerical Method (Finite Difference)
– Polynomial Fit

6
Numerical Method (Finite Difference)
- Can be used when the data points in the independent variable are equally spaced: t1-t0 = t2 – t1 = t

Time t0 t1 t2 t3 t4 t5

Concentration CA0 CA1 CA2 CA3 CA4 CA5

- The three-point differentiation formulas:

Initial Point:  dC A  −3C A0 + 4C A1 − C A2

  =
 dt t0 2t

 dC A  1
Interior point:   = C A( i +1) − C A( i −1) 
 dt ti 2t
 dC  1
e. g.,  A  = C A 4 − C A 2 
 dt t 3 2t

Last point:  dC  1
e. g.,  A  = C A3 − 4C A4 + 3C A5 
7  dt t 5 2  t
Polynomial Fit

1. Fit the Conc.-time data to an nth–order polynomial (Polymath)

C A = a0 + a1t + a2t 2 + ... + ant n

2. Differentiate w.r.t. time:

dC A
= a1 + 2a2t + 3a3t 2 + ... + nant n −1
dt

Example 5-1

8
 Integral Method
dCA
 Guess the reaction order and integrate the diff. equation − = kCA
dt
 If the order we assume is correct, the appropriate plot(determined from
the integration) of the data should be linear.


The integral method is used most often when the reaction order is known
and it is desired to evaluate k(T) and Ea.

9
 Integral Method
Zero order First order Second order

 dC A   dC A   dC A 
  = rA = − k   = rA = − kC A   = rA = − kC A
2

 dt   dt   dt 
CA t CA t CA t
dC A dC A
 dC A = − k  dt C C A = −k 0 dt C C A 2 = −k 0 dt
C A0 0 A0
A0

C A − C A0 = − kt ln C 
CA
CA
= − kt  1 
A C A0 −   = − kt
C A = C A0 − kt ln C A − ln C A0 = − kt  C A  C A0
ln C A0 − ln C A = kt  1 1 
− −  = − kt
 C A0   C A C A0 
ln   = kt  1 1 
 CA   −  = kt
10  C A C A0 
 Integral Method Example 5-2

Guess and check for α = 0, 1, 2 and check against experimental plot.

 = 0:  = 1:  = 2:
 C A0  1 1
C A = C A0 − kt ln   = kt − = kt
 CA  C A C A0

11
 1 1
 = 2: − = kt
C A C A0

12
 Non-Linear Least-Square Analysis
We want to find the parameter values (α, k, E) for which the sum of
the squares of the differences, the measured rate (r m), and the
calculated rate (rc) is a minimum.

( rim − ric )
2
n
S2
2 =  =
i =1 N −K N −K

We find the values of  and k which minimize 2

13
 Least Squares Regression
Linear Regression : Notation
 (x1, y1), (x2, y2), . . . , (xn, yn)
 draw the line y= b0 + b1x through the
scatterplot , the point on the line corresponding
to xi is
𝑦ො𝑖 = 𝑎0 + 𝑎1 𝑥𝑖 ; 𝑦ො𝑖 is the value of y predicted by the line
y = 𝑎0 + 𝑎1 𝑥 when 𝑥 = 𝑥i ;
𝑦𝑖 is the observedvalue of 𝑦 𝑥 = 𝑥i .
 FUEL CONSUMPTION vs CAR WEIGHT

7
FUEL CONSUMPTION

6.5

5.5
predicted y when
5 x=2.7
yhat = a + bx
= a + b*2.7
4.5

4 (2.7, 3.6)
3.6 = observed y
3.5

2.5

2
1.5 2 2.5 3 3.5 4 4.5

CAR WEIGHT
 Linear Regression: Question
How to find a0 and a1 so that the error would be
minimum?
The residual is the vertical deviation of the data
point from the line:

n n
min  ei =  ( yi − a0 −a1 xi ) Criteria for
i=1 i=1 a “Best” Fit
16 Salaheddin Abu Yahya 5/30/2021
 Linear Regression: Least Squares Fit
n n n
S r =  e =  ( yi , measured − yi , model) =  ( yi − a0 − a1 xi ) 2
2
i
2

i=1 i=1 i=1

n n
min Sr = 
i=1
ei2 = 
i=1
( yi − a0 − a1xi)2

Yields a unique line for a given set of data.

The coefficients a0 and a1 that minimize Sr must

satisfy the following conditions:
 Linear Regression:
Determination of ao and a1

2 equations with 2
unknowns, can be solved
simultaneously
 Linear Regression:
Determination of ao and a1

n  xi yi −  xi  yi
a1 =
n xi − ( xi )
2 2

Mean values

a0 = y − a1 x
 Least Squares Fit of a Straight Line:

Fit a straight line to the x and y values in the

following Table:

xi yi xiy i xi2  xi = 28  yi = 24.0

1 0.5 0.5 1
2 2.5 5 4
 xi2 = 140  xi yi =119.5
3 2 6 9
28
4 4 16 16 x= =4
5 3.5 17.5 25 7
6 6 36 36
24
7 5.5 38.5 49 y= = 3.428571
7
28 24 119.5 140
Least Squares Fit of a Straight Line: Example
(cont’d)

n xi y i −  xi  yi
a1 =
n x − ( xi )
2 2
i

7119.5 − 28 24
= = 0.8392857
 7 x140 − 282
 a0 = y − a1x
 = 3.428571− 0.8392857 4 = 0.07142857
Y = 0.07142857 + 0.8392857 x
 Example (2)

7
y = 0.8393x + 0.0714
6

4
Y

0
0 2 4 6 8
x
 Error Quantification of Linear Regression
• Sum of the squares of residuals around the
regression line is Sr
 For concentration-time data, we can combine the mole balance equation
for −rA = kCA to obtain:
dC A
= −kC A
dt
t = 0 : C A = C A0

Integrating: C1A−0 − C1A− = (1 −  )kt

Rearranging to obtain the calculated concentration as a function of time,

we obtain:
C Ac = C A = [C 1A−0 − (1 −  )kt ]1/(1− )

24
Now we could use Polymath or MATLAB to find the values of α and k that would
minimize the sum of squares of differences between the measured (CAm) and calculated
(CAc) concentrations.
That is, for N data points,

If Polymath is used, one should use the absolute value for the term in brackets

Similarly one can calculate the time at a specified concentration, tc

and compare it with the measured time, tm, at that same concentration.
That is, we find the values of k and α that minimize:

Example 5-3
25
 Method of Initial Rates
 Used when reactions are reversible.
 A series of experiments is carried out at different initial concentration, CA0, and
the initial rate, -r
A0
 dC 
=  A , is determined for each run using:
 dt 0

1. Graphical: find the slope of the CA vs. t curve at t = 0 for each run.
2. Finite difference formula:
 dC A  −3C A0 + 4C A1 − C A2
  =
 dt t0 2t
3. Polynomial fit:
C A = a0 + a1t + a2t 2 + ... + ant n

dC A
= a1 + 2a2t + 3a3t 2 + ... + nant n −1
dt

 dC A 
  = a1
26
 dt t =0
 
 If the rate law of the form − rA0 = k AC A0 is combined with the
mole balance then

dC A0  dC 
− = − rA0 = k AC A0 ln  − A  = ln k A +  ln C A0
dt  dt 0

 The slope of the plot ln (-rA0) vs. ln (CA0) will give the rxn order
.

See Example 5-4

27
 Differential Reactors
 Most commonly used catalytic reactor to obtain experimental data
 It consists of a tube containing a very small amount of catalyst

 The conversion of the reactants is very small → CA  constant = CA0

→ Gradient  0 → uniform rxn rate within the bed
→the design equation is similar to the CSTR.

28
 - A steady-state mole balance on reactant A gives:
[in] – [out] + [gen] = [acc]
FA0 − FAe + rA W = 0

FA0 − FAe 0C A0 −  C Ae FA0 X FP

− rA = or − rA = or − rA = =
W W W W
- The term FA0X gives the rate of formation of the product, FP, when the stoichiometric
coefficients of A and of P are identical.
0 ( C A0 − C Ae ) 0CP
- For constant volumetric flow rate: − rA = =
W W
→ The reaction rate can be determined by measuring the product concentration, CP.

- By using very little catalyst and large volumetric flow rate: CA0 - CAe  small, then
the reactant concentration in the catalyst bed CAb  CA0

- Then, the rate can be obtained as a function of CA0: −rA = −rA (CA0 )

29 Read Example 5-4

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