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Engineering

Interpretation of Lab Reactor

Data (to obtain Rate Laws)

Dr Veluri VPS Murthy, Professor

Phone: +606 7989 271 (preferred)

Mobile: +601116672959

e-mail: vvpsnm@gmail.com

Chemical Reaction Engineering

2014

Contents

Reaction Kinetics & Rate Law (Recap)

Measurement of concentrations

Methods of Data Analysis to obtain Rate Laws of

homogeneous reactions

Integral method

Differential method (using Batch and CSTR)

Method of initial rates

Method of half-lives.

(Recap)

Concentrations

Temperature

Pressure

rate of a reaction.

Rate law is a function of concentration and

temperature (through the rate constant, k)

-rA= [k(T)] [f(CA, CB, ...)]

3

(Recap)

only if the stoichiometric coefficients are the

same as the individual reaction order of each

species.

For example, if the reaction aA+bB cC + dD, is

elementary, the rate law would be: -rA=kACAaCBb

a order with respect to A

b order with respect to B

If 2NO+O2 2NO2

then -rNO = kNO C 2 NO CO2 if it is elementary!

f(CA) is determined experimentally.

4

Weve seen how to write rate laws once we have a

reaction mechanism for elementary reactions.

It is important to check whether the proposed rate

law agrees with the experimentally-determined

rate law.

Now, well learn the methods for determining rate

laws from batch experiments using

Concentration versus time data from a constant volume

batch reactor.

rate laws of homogeneous reactions.

5

Measurement of concentrations

In a batch reactor, the concentrations change with

time continuously. Hence, concentrations of

reactants have to be measured.

Some of the techniques to measure concentrations are as follows:

Pressure measurements

Spectroscopic measurements (IR, UV, Vis)

Electrical measurements (conductivity, etc)

these measurements is mathematically analyzed

to determine the kinetics i.e. rate law.

6

Rate Laws from Batch Reactor Data

Various methods of analysis of data are:

Integral method

Differential method

Method of initial rates

Method of half-lives

Excess if the reaction has multiple

reactants.

7

Integral Method

In this method, we integrate the design equation.

It is a trial and error method.

Most often used when reaction order is known

and we need to find k.

This method is considered for zero, first and

second order reactions.

Method: Integrate the design equation assuming

the order and rearrange to a linear form.

Use the concentration Vs. time data to calculate

the variables in the rearranged form and plot.

If the data fit shows linearity, it confirms the order

assumption and k is determined from the slope.

8

1. General Mole Balance

2. Rate Law

dNA

(rA ) V

dt

(rA ) k CA

3. Stoichiometry

V=Vo

system

4. Combine 1 dN A dC A (r )

A

with -rA

V dt

dt

CA

CA0

and carry out the integration

and plot the data.

9

t t

dC A

dt

kCA t 0

assumption

( rA ) k C k C k

0

A

dC A

k

dt

t t

CA

dC A

dt t 0 t

k t 0

C A0

CA

1

1

1

CA

C A C A 0 C A C A0 t

dC A

k C A0

k

k

C A C A0 kt

C A C A0 kt

10

( rA ) k C A k C A

CA

C A0

dC A

k CA

dt

t t

dC A

dt t 0 t

kCA t 0

CA

1

dC A

1

1

CA

ln C A C A0 ln C A ln C A0 t

k C A0 C A

k

k

ln C A / C A0 kt

ln C A0 / C A kt

11

assumption

( rA ) k C A k C A2

dC A

2

k CA

dt

t t

CA

dC A

dt t 0 t

2

C A 0 kCA

t 0

CA

1

dC A

1

1

k CA0 C A

k CA

CA

C A0

1 1

1

t

k C A C A0

1

1

kt

C A C A0

1

1

kt

C A C A0

12

assuming 0th , 1st and 2nd order

Zero-order

First-order

Second-order

13

Data acquired from batch reactor experiment

t [min]

CA

2.0

1.60 1.35

15

22

1.10 0.87

30

40

0.70 0.53

60

0.35

[mol/L]

Start with zero-order

14

Zero-order: CA=CAO-kt

t [min]

CA

0 5

15

22

30

40

60

0.53

0.37

[mol/L]

Integral Method- zero order

2.50

CA (mol/L)

2.00

y = -0.026x + 1.6508

2

R = 0.8621

1.50

1.00

0.50

0.00

0

10

20

30

40

time, min

50

60

15

70

First-order ln C A 0 kt

CA

t [min]

0 5

ln CA0 / CA 0 0.22

15

22

0.39

0.64 0.92

30

40

60

1.05

1.33

1.69

2.50

y = 0.032x

2

R = 0.9638

ln(CA0/CA)

2.00

1.50

1.00

0.50

0.00

0

10

20

30

40

time, min

50

60

16

70

1

1

kt

CA

CA0

Second-order

t [min]

1 / CA

15

22

30

40

60

1.89

2.70

3.00

2.50

1/CA

2.00

1.50

y = 0.039x + 0.3793

2

R = 0.9852

1.00

0.50

0.00

0

10

20

30

40

time, min

50

1760

70

Differential Method

It is called differential method, because we

differentiate the concentration versus time data.

Determines reaction order directly

no trial and error (like integral method)

the rate is essentially a function of the

concentration of only one reactant.

aA products

Assume that the rate law is of the form:

-rA= kA CA

18

1. General Mole Balance

2. Rate Law

(rA ) k CA

3. Stoichiometry V=Vo

4. Combine

dNA

(rA ) V

dt

1 dNA

(rA )

V dt

dC A

k CA

dt

19

dCA

k CA

dt

dC A

ln(

) ln(k ) ln(C A )

dt

(CA).

ln (-d CA/dt)

of the above equation,

ln (CA).

from intercept

20

Alternatively, Reaction order

dCA

ln(

) ln(k ) ln(C A )

() can be found from slope of

dt

log-log plot of - dCA/dt and CA

(- dCA/dt)

1000

100

dCA

dt p

10

CA

1

1

10

100

1000

CA

21

dCA

dt

CA

Determination of Derivative

In order to carry out the Differential Method, it is

necessary to calculate the derivatives from the

concentration Vs. time data.

There are 3 different methods to determine the

derivative.

Graphical method

Numerical Method

Polynomial Method

22

Graphical Method

Determination of Derivative

Derivative by building tangents is prone to errors.

CA

time

Determine CA for each time interval and calculate CA /

t.

Plot this CA / t against time.

Read - dCA/dt at t for which corresponding CA has

been measured.

23

[CA vs t] data Graphical Method

Step 1: Calculate CA & t

Step 2: Plot - CA / t vs t

for which corresponding

CA has been measured

1.6

1.4

-dC/dt

1.2

1

0.8

0.6

0.4

0.2

0

0

10

15

20

t [min]

24

Numerical Method

Determination of Derivative

Can be used, when data points are equally spaced

such as t1 - t0 = t2 - t1= t

The three point differentiation formulas can be used.

Initial point

3C A 0 4C A 1 C A 2

dC A

)t 0

dt

2 t

Intermediate points

(

Last point

dC A

1

)ti

dt

2 t

A ( i 1)

C A (i 1)

C A (n2 ) 4C A (n1) 3C A (n )

dC A

(

)tn

dt

2 t

25

Polynomial method

Determination of Derivative

Step 1: Fit CA vs t data using a polynomial of

n th order: (many software packages can do that)

CA = ao +a1t +a2t2+ an tn

Step 2: After determining the polynomial, it has to

be differentiated with respect to time

i.e. Calculate dCA /dt

dCA /dt = a1 + 2 a2t+ (n) an tn-1

26

Summary

Rate laws can be determined experimentally in many ways.

Integral Method

Integrate the design equation and rearrange.

Determine whether the data fits the proposed line.

Trial and error.

Differential Method

Suitable to irreversible reactions with one reactant only.

Must find the derivative, dCA/dt

Not trial and error.

Excess to find reaction order for each.

To be done: Method of Initial Rates and Method of Half-Lives

27

Tutorial #8

1. Integral method

t [min]

12

2.50 2.00

15

18

21

(order & rate constant) of the reaction.

2. Differential method

Determine the rate law of reaction using the

numerical method and the polynomial method

t [min]

12

15

CA

[mol.L-1]

15

11.0

8.0

6.0

4.5

3.5

28

Rate Law using a CSTR

FA0

CA0

FA0 FA (rA ) V 0

2. Rate Law

3. Stoichiometry

FA

CA

(rA ) k C A

v = vo

4. Combine

v0 [C A0 C A ] ( rA ) V

v0 [C A0 C A ]

(rA )

V

29

A CSTR is being used to determine the kinetics of

a reaction whose stoichiometry is A R.

For this purpose, various flow rates of an aqueous

solution of 100 mmol/L of A are fed to a 1.0 L

reactor, and

For each run the outlet concentration of A is

measured.

Find a rate expression to represent the following

data. (Assume that reaction is irreversible.)

v0 (L/min)

CA (mmol/L)

1

4.5

6

19

24

53

30

Data Treatment

v0 (L/min)

CA (mmol/L)

1

4.5

CA

v0

(L/min) (mmol/L)

1

4.5

6

19

24

53

6

19

24

53

CA0-CA

(mmol/L)

95.5

81

47

v0 [C A0 C A ]

(rA )

V

(-rA)

(mmol/L-min)

95.5

486

1128

31

8.0

7.0

ln (-rA)

6.0

5.0

y = 1.009x + 3.092

R2 = 0.993

4.0

3.0

Slope = = 1

2.0

1.0

0.0

0.0

1.0

2.0

3.0

4.0

ln (CA)

k = exp(3.092) min-1

= 22.021 min-1

32

5.0

Differential method is the most simple, but could

be ineffective if the reaction is reversible.

Unlike differential and integral methods, the

method of initial rates requires a series of

experiments instead of just one.

Carry out experiments at different initial

concentrations CAO and determine the initial rate

of reaction -rAO. Then plot to find rate law.

e.g. -rAO= (-d CA0/dt) = kCAO

ln (-rAO)= ln (-d CA0/dt) = ln (k) + ln(CAO)

33

ln (-d CA0/dt)

ln (CA0)

Intercept = ln (k)

Similar to differential method.

34

The dissolution of dolomite (calcium magnesium

carbonate) is a reaction important in the acid

stimulation of dolomite oil reservoirs.

4HCl + CaMg(CO3)2 Mg2+ + Ca2+ + 4Cl- + 2CO2 + 2H2O

various times from AAS of the calcium and

magnesium ions.

The rate law for the initial rate can be written as

dCHCl

dt

(rHCl )0 kCHCl

,0

0

35

(Example)

Determine the reaction order with respect to HCl

from the data presented below !

1M HCl

4M HCl

Run 2

4.0000

1.0000

3.9990

0.9990

C (HCl)

C (HCl)

Run 1

3.9980

0.9980

3.9970

0.9970

3.9960

0.9960

t [m in]

t [m in]

36

Taking logarithms of both sides of the rate law equation, we

have

dCHCl

dt

(rHCl )0 kCHCl

,0

0

dCHCl

ln

dt

ln k ln CHCl,0

0

plot of concentration versus time at t = 0. Or, by using the

formula for initial point as in the differential method.

3C A 0 4C A 1 C A 2

dC A

(

)t 0

dt

2 t

CA

time

37

(Example)

For a set of 4 experiments, using 4 different initial

concentrations, we would generate the following data set:

time [min]

C(A)

C(A)

C(A)

C(A)

4.00

1.00

2.00

0.1000

3.86

0.965

1.93

0.0960

3.75

0.93

1.87

0.0935

3.65

0.90

1.81

0.0915

3.55

0.87

1.75

0.0900

38

Method of

Half-life (t1/2) is the time taken for the concentration to

drop to 1/2 of the initial value.

We can find and k by finding t1/2 as a function of CAO.

rA k A C

t t

CA

CA 0

CA

CA

dC A

k A C A

dt

dCA

dt t 0 t

kC A

t 0

dCA

1

1 C

t

C A dC A

kC

k

k

(

1

)

A

CA 0

CA 0

1

A

CA

CA 0

1

1

k( 1) CA1

39

CA

CA 0

Method of Half-Lives

1

1

t

k( 1) CA1

CA

CA 0

1

1

1

1 1

k( 1) C A

CA0

C

1

t

kCA01( 1) C

1

A0

1

A

1

1

C

1

A0

kC A 0 ( 1) C A

1/2 of the initial value.

i.e. CA = CA0 /2 when t = t . Substituting this in the eqn above,

1

CA0

1

t 1/ 2

1

1

kC A 0 ( 1) (1/ 2)C A 0

t 1/ 2

1

2 1

1

2 1

1

kC A 0 ( 1)

k( 1)CA01

40

Method of Half-Lives

Taking logarithms of both sides of the equation, we have

t 1/ 2

k( 1)CA01

ln t 1/ 2

2

ln

1

(1 )lnC A 0

k( 1)

at different initial concentrations have to be conducted.

Slope = 1-. From the Intercept, k can be found. Not suitable

for 1st order.

ln t 1/ 2

ln CA0

41

Method of Excess

Method of excess can be used with all methods.

e.g. A + B products

-rA=kACACB

We run our reaction twice

First with excess B, so CB=CBO=constant through entire

reaction.

Then -rA=k CA where k=kACBO

entire reaction..

Then -rA=k CB where k=kACAO

rA

kA

C A CB 42

Experimental Planning

4 to 6 weeks in the lab can save you 1 hour in the

library G.C. Quarderer, Dow Chemical

Examine the need for the experiment

Define objectives

Choose responses you measure

Identify important variables

Perform experiment

Analyze results

Act on results

43

PDCA

PLAN

Step 2 Plan activity schedule

DO

CHECK

ACTION

situation

Step 4 Set target

Step 5 Identify causes & propose

solutions

44

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