5.

Collection and Analysis of Rate Data

Objectives: After completing Chapter 5, you will be able to: Determine the reaction order and specific reaction rate from experimental data obtained from either batch or flow reactors. Describe how to use equal-area differentiation, polynomial fitting, numerical difference formulas and regression to analyze experimental data to determine the rate law. Use regression to evaluate the rate law parameters given experimental data. Describe how the methods of half lives, and of initial rate, are used to analyze rate data.

Finding the Rate Law Data for homogeneous reactions is most often obtained in a batch reactor. The usual procedure is to collect concentration time data, which we then use to determine the rate law.

Steps in Analyzing Rate Data: 1. Postulate a rate law. Power law models for homogeneous reactions, e.g. ; 2. Select reactor type and corresponding mole balance. If batch reactor, use mole balance on Reactant A

3. Process your data in terms of measured variable (e.g., NA, CA, or PA). If necessary, rewrite your mole balance in terms of the measured variable (e.g.. PA) 4. Look for simplifications. For example, if one of the reactants in excess, assume its concentration is constant. If the gas phase mole fraction of reactant is small, set . By utilizing the method of excess, it is possible to determine the relationship between -rA and the concentration of reactants. For the irreversible reaction A + B Products with the rate law

where and are both unknown, the reaction could first be run in an excess of B so that CB remains essentially unchanged during the course of the reaction and where After determining , the reaction is carried out in an excess of A, for which the rate law is approximated as where Once and are determined, k can be calculated from the measurement of -rA at known concentrations of A and B: ( ) Both and can be determined by using the method of excess, coupled with a differential analysis of data for batch systems. 5. For a batch reactor, calculate -rA as a function of concentration CA, to determine reaction order.

A. Differential analysis Combine the mole balance and power law model, e.g.

And then take the natural log. ( (1) Find ) from CA versus t data by

(a) Graphical method Read Appendix A.2.

This method accentuates measurement error!

(b) Finite differential method Numerical differentiation formulas can be used when the data points in the independent variable are equally spaced, such as :

The three-point differentiation formulas can be used to calculate . Initial point:

Interior points:

Last point:

(c) Polynomial First fit the concentration-time data to an nthorder polynomial:

After determining the constants, ai, one has only to differentiate the equation with respect to time:

Thus concentration and the time rate of change of concentration are both known at any time t. 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 and not go through many of the points. 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.

Using either the graphical method, differentiation formulas, or the polynomial derivative, the following table can be set up:

( ) versus (2) Plot and find reaction order , which is the slope of the line fit to the data.

(3) Find k.

B. Integral method The integral method uses a trial-and-error procedure to find reaction order. Combine the mole balance and power law model, e.g.

(1) Guess and integrate the equation. Rearrange your equation to obtain the appropriate function of CA, which when plotted as a function of time should be linear. Zero Order First Order Second Order

If it is linear, then the guessed value of is correct and the slope is specific reaction rate, k. If it is not linear, guess again for .

Note: 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. If you guess and none of these orders fit the data, such as

then we should stop guessing reaction orders and proceed to nonlinear regression. (2) Nonlinear regression. Integrate the equation to obtain [ or [
( ) (

(
)

) ] ] untuk

We want to find the parameter values (e.g. and k) for which the sum of the squares of the differences between the measured parameter (Pm) and the calculated parameter (Pc) is a minimum. where N = number of runs ( )

K = number of parameters to be determined That is we want to be a minimum. Measured data: Time (s) 0 t1 t2 t3 Concentration (mol/L) CA0 CA1 CA2 CA3 Thus: or We now guess k and , and calculate each CAci at the times shown in the above table and then compare it with the measured concentration by taking the difference and squaring it. We then sum up the differences for all the data points. ( ( [ or ( ) ] ) )

( (

)
( ) ( )

])

We continue to guess k and until we find the values of k and which minimize s2 (actually we let the computer find these values.)

6. Analyze your rate law model for "goodness of fit. Calculate a correlation coefficient. One can also determine which model or equation best fits the experimental data by comparing the error for each model and then choosing the equation with a smaller error. Problem 5.1.

The reaction

is carried out in a constant volume batch reactor. Determine the reaction order and specific reaction rate from the following data. t (min) 0 10 20 30

CA(mol/dm3) 1 0.6 0.4 0.3 Solution:

t 0

CA 1 0.4 -(0.6-1.0)/(10-0)=0.04

10 0.6 0.2 20 0.4 -(0.4-0.6)/(20-10)=0.02

0.1 30 0.3 First find

-(0.2-0.4)/(30-20)=0.01

t 0

CA 1 0.053

10 0.6 0.028 20 0.4 0.017 30 0.3 0.014

2) Combined mole balance and postulated rate law is

taking the natural log of both sides

Plot versus ln CA or plot versus CA on log-log paper to determine the reaction order.

The reaction order is

therefore,

When CA=1.0 mol/dm3 then

Or use linear regression:

Dengan ( ); ; ;

Persamaan untuk menghitung a dan b: ( )

CA

0 1 10 0,6 20 0,4 30 0,3 Sum

-dCA/dt y x xy x^2 0,053 -2,937 0,000 0 0,000 0,028 -3,576 -0,511 1,826 0,261 0,017 -4,075 -0,916 3,733 0,840 0,014 -4,269 -1,204 5,139 1,450 -14,856 -2,631 10,699 2,550

N= a= b= k=

4 1,132 -2,97 0,051

Problem 5.2. Solve Problem 5.1. using the integral method. Answer: Check for .

Integrate for [ For :

: ( ) ]

For

: [ ]

For

: [ ]

For

: ( )

Zeroth Order: t CA 0 10 20 30

1,2

1 0,6 0,4 0,3

1 0,8 0,6 0,4 0,2 0 y = -0,023x + 0,92 R = 0,92

10

20

30

40

First Order: t CA ln(CA0/CA) 0 1 0 10 0,6 0,510826 20 0,4 0,916291 30 0,3 1,203973

1,4

1,2
1 0,8 y = 0,040x + 0,055 R = 0,984

0,6
0,4 0,2 0

10

20

30

40

Second Order: t CA 1/CA 0 1 1 10 0,6 1,666667 20 0,4 2,5 30 0,3 3,333333

3,5

3
2,5 2 y = 0,078x + 0,95 R = 0,997

1,5
1 0,5 0

10

20

30

40

Third Order: t CA 1/CA^2 0 1 1 10 0,6 2,777778 20 0,4 6,25 30 0,3 11,11111

12 10 8 6 4 2 0

y = 0,338x + 0,213 R = 0,96

10

20

30

40

From correlation coefficient, we know that the best model is second order reaction, with k = 0,078 min-1. Alternative solution: Calculate k for each model. For :

For

: ( )

For

For

Order: t CA 0 1 10 0,6 20 0,4 30 0,3 Mean Rata2 persen ralat thd mean

1 k 0,0511 0,0458 0,0401 0,0457

0,0400 0,0300 0,0233 0,0311

0,0667 0,0750 0,0778 0,0731

0,0889 0,1313 0,1685 0,1296

57,14

24,28

17,72

62,78

Study Example 5.1, 5.2, 5.3, dan 5.4 Fogler

Method of Initial Rates This method is used when reactions are reversible. 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, -rA0, can be found by differentiating the data and extrapolating to zero time. If the rate law is in the form the slope of the plot of ( will give the reaction order . Method of Half-Lives The half-life of a reaction, , is defined as the time it takes for the concentration of the reactant to fall to half of its initial value. If two reactants are involved in the reaction, the experimenter will use the method of excess in conjunction with the method of half-lives to arrange the rate law to the form: ) versus

For an irreversible reaction, A Products, a mole balance on species A in a constant-volume batch reaction system combined with the rate law results in the following expression:

Initial condition: t = 0, CA = CA0. Integrate the equation:

At

Substituting for CA in the equation gives us

There is nothing special abut using the time required for the concentration to drop to one-

half of its initial value. We could just as well use the time required for the concentration to fall to 1/n of the initial value, in which case

For the method of half-lives,