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Example - Finding The: Rate Law

This document discusses various methods for determining the rate law of a chemical reaction from experimental concentration-time data: 1) The method of initial rates involves measuring the initial reaction rate at different initial concentrations and determining the reaction order from the slope of a plot of rate vs. concentration. 2) The method of half-lives determines the half-life of the reaction at different initial concentrations to deduce the reaction order and rate constant. 3) Non-linear least squares analysis fits the integrated rate law equation to concentration-time data to minimize errors and estimate kinetic parameters. 4) Differential reactors use small concentration changes to directly measure initial rates and determine kinetics via the method of initial rates.

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hossein
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40 views

Example - Finding The: Rate Law

This document discusses various methods for determining the rate law of a chemical reaction from experimental concentration-time data: 1) The method of initial rates involves measuring the initial reaction rate at different initial concentrations and determining the reaction order from the slope of a plot of rate vs. concentration. 2) The method of half-lives determines the half-life of the reaction at different initial concentrations to deduce the reaction order and rate constant. 3) Non-linear least squares analysis fits the integrated rate law equation to concentration-time data to minimize errors and estimate kinetic parameters. 4) Differential reactors use small concentration changes to directly measure initial rates and determine kinetics via the method of initial rates.

Uploaded by

hossein
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 14

5/14/2016

Lecture 15

Example Finding the Rate Law


t(min)

CA(mol/L)

0.7

0.5

0.35

C A
t

0.3

0.2

C A
t .3
.2

0.15

Areas equal for both


sides of the histogram

.1

5/14/2016

Example Finding the Rate Law


Find f(t) of
CA
-dCA/dt

C A
using equal area differentiation
t

1
0.35

0.7
0.25

0.5
0.175

0.35
0.12

Plot (dCA/dt) as a function of CA


ln
dCA/dt

Slope =
ln

CA

Example Finding the Rate Law


Choose a point, p, and find the concentration and
derivative at that point to determine k.

dC A

dt p
k
C Ap

ln dCA/dt
dC A

dt p

Slope =
CA p

ln CA

5/14/2016

Linear Least-Square Analysis


In the case where the rate law is dependent on

the concentration of more than one reactants and


method of excess is not applicable.

dC
r kC C
dt

dC
) r kC C
dt

ln (
5

A0

A0

B0

dC
) ln k ln C ln C
dt
A

A0

B0

Linear Least-Square Analysis


ln (

dC
) ln k ln C ln C
dt
A

A0

B0

Y ln( dC / dt ) , X ln C , X ln C , a ln k , a
A

Y a a X a X
0

A0

j 1

1j

j 1

2j
N

X Y a X a X a X X
j 1

1j

j 1

Y Na a X a X
j 1

B0

1j

j 1

1j

1j

j 1

2j

X Y a X a X X a X
j 1

2j

j 1

2j

j 1

1j

2j

j 1

2
2j

5/14/2016

Non-Linear Least-Square Analysis


We want to find the parameter values (, k, E) for
which the sum of the squares of the differences, the
measured rate (Cm), and the calculated rate (Cc) is
a minimum.
n
2


i 1

Cim Cic 2
N K

That is, we want

S2
N K

2 to be a minimum.

For concentration-time data, we can combine the


mole balance equation for rA kCA to obtain:
dC A
kC A
dt
t 0 C A C A0

Rearranging to obtain the calculated concentration


as a function of time, we obtain:
C 1A0 C 1A (1 )kt

C Ac C A [C1A0 (1 ) kt ]1/(1 )
8

5/14/2016

Now we could use Polymath or MATLAB to find the values of 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,

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 that minimize:

Example

Find reaction order and specific reaction rate by nonlinear


least square analysis.
10

5/14/2016

11

Method of Initial Rates


A series of experiments are carried out at different

initial concentrations, CA0 and initial reaction rate


rA0 is determined for each run.
The initial rate can be found by differentiating the

data and extrapolating to zero time.

12

5/14/2016

Example

13

Solution

14

5/14/2016

15

Method of Half-Lives
The half-live of a reaction is the time it takes for the

concentration of the reactant to fall to half of its initial value.


By determining the half-life as a function of the initial

concentration, the reaction order and constant can be


determined.
If two reactants are involved, use the method of excess in

conjunction with the method of half-lives to arrange the rate


of the form:

16

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17

18

5/14/2016

Differential Reactors

19

20

10

5/14/2016

Using very little catalyst and large volumetric flow rates:

CA0-CAe can be made quite small

Use method of initial rates to find reaction order and specific

reaction rate.
21

Example
T=500 F

22

11

5/14/2016

23

Solution

24

12

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25

26

13

5/14/2016

27

14

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