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1

Kinetics and Reaction Rate

What is reaction rate?

It is the rate at which a species looses its

chemical identity per unit volume.

The rate of a reaction can be expressed as:-

- The rate of disappearance of a reactant or

- The rate of appearance of a product.

2

YA1

Reaction Rate

Consider species A:

rB = the rate of formation of species B per unit volume

EXAMPLE: If B is being formed at 0.2 moles per decimeter

cubed per second, ie, rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s

The rate of formation (generation of A) is rA= -0.2

mole/dm3/s

3

Slide 3

YA1 Y A, 4/5/2008

Reaction Rate

Consider species j:

rj is the rate of formation of species j per unit

volume [e.g. mol/dm3*s]

rj is a function of concentration, temperature,

pressure, and the type of catalyst (if any)

rj is independent of the type of reaction system

(batch, plug flow, etc.)

rj is an algebraic equation, not a differential

equation

4

Rate Law Basics

A rate law describes the behavior of a

reaction. The rate of a reaction is a

function of temperature (through the rate

constant) and concentration.

5

Reaction Rate for solid catalytic reactions

is the rate of disappearance of species A on a

per mass of catalyst basis.

-r'A = rA/bulk density of the catalyst (b)

6

Rate Law Basics

A rate law describes the behavior of a reaction. The rate

of a reaction is a function of temperature (through the

rate constant) and concentration.

Power Law Model

k is the specific reaction rate (constant)

k is given by the Arrhenius Equation:

R = gas constant (cal/mol*K)

T = temperature (K)

A = frequency factor (units of A, and k, depend on overall

reaction order)

7

General Mole Balance

8

Batch Reactor Mole Balance

9

Constantly Stirred Tank Reactor Mole Balance

CSTR or MFR

10

Plug Flow Reactor (PFR) Mole Balance

FA dF A

The integral form is: V=

FA 0 rA

flow rate (mol/s) from FA0 to the exit molar flow rate of FA.

11

Packed Bed Reactor Mole

Balance

PBR

dN A

FA0 FA + rA dW =

dt

FAdFA

The integral form to find the catalyst weight is: W=

FA 0 rA

12

Space time and space velocity

FA0 = CAo vo

= is called space time (s) = V/vo

Space velocity = 1/, where;

FA0 = Molar feed rate of key reactant A (mol/s)

CAo= Concentration of key reactant A in the feed

(mol/m3)

vo=Volumetric flow rate of feed to the reactor (m3/s)

V = volume of the reactor

For constant volume systems v = vo where v is

volumetric flow rate leaving the reactor

13

Reactor Mole Balance Summary

14

Reactor Mole Balance

Summary

15

Reactor Mole Balance

Summary

16

Reactor Mole Balance

Summary

17

Reactor Mole Balance

Summary

18

Conversion

Consider the general reaction: aA + bB -cC + dD

We will choose A as bases of calculation (i.e. Key reactant)

The limiting reactant is usually taken as the key reactant

Then: A + (b/a)B (c/a)C + (d/a)D

XA = moles reacted/moles fed

19

Batch Reactor Conversion

dN A

= rA V

dt

20

CSTR Conversion

Algebraic Form:

21

PFR Conversion

dF A

PFR

= rA

dV

FA = F A0 (1 X)

Differential Form:

Integral Form:

22

Design Equations

23

Reactor Sizing (CSTR)

Given -rA as a function of conversion, -rA=f(X), one can size any

type of reactor.

We do this by constructing a Levenspiel plot.

Here we plot either FA0 or 1 as a function of X.

r A r A

volume of a CSTR is: F A0 (X 0 )

V=

rA

EXIT

24

Reactor Sizing (PFR)

For PFR th evolume of the reactor needed is

given by the area under the curve

X F

V PFR = 0 rA

A 0

dX

=area

25

Summary

26

Rate Law Basics

A rate law describes the behavior of a

reaction. The rate of a reaction is a

function of temperature (through the rate

constant) and concentration.

k is the specific reaction rate (constant)

27

Examples of Rate Laws

First Order Reactions

(1) Homogeneous irreversible elementary gas phase reaction

C2H 6 C2H 4 + H 2 82kcal 1

1

1 mol 1000 T

rA = kC C 2 H 6 with k = 0.072s e

28

Examples of Rate Laws

First Order Reactions

(1) Homogeneous irreversible elementary gas phase reaction

C2H 6 C2H 4 + H 2 82kcal 1

1

1 mol 1000 T

rA = kC C 2 H 6 with k = 0.072s e

n C 4 H10 i C 4 H10

[

rn = k C nC 4 CiC 4 K C ]

T 360 T 333

k = 31.1exp 7906 K C = 3.03exp 830.3

with 360T

and 333T

29

Examples of Rate Laws

First Order Reactions

(1) Homogeneous irreversible elementary gas phase reaction

C2H 6 C2H 4 + H 2 82kcal 1

1

1 mol 1000 T

rA = kC C 2 H 6 with k = 0.072s e

n C 4 H10 i C 4 H10

[

rn = k C nC 4 CiC 4 K C ]

T 360 T 333

k = 31.1exp 7906 K C = 3.03exp 830.3

with 360T

and 333T

(1) Homogeneous irreversible non-elementary reaction

m3 cal

with k = 0.0017 and E = 11273 At 188C

kmol.min mol

rA = kC ONCBC NH3

This is first order in ONCB, first order in ammonia and overall second order.

30

Examples of Rate Laws

Second Order Reactions

(2) Homogeneous irreversible elementary reaction

CNBr + CH 3 NH 2 CH 3 Br + NCNH 2 with 2.2dm 3

k=

s.mol

rA = kC CNBr C CH 3 NH 2

31

Examples of Rate Laws

Second Order Reactions

(2) Homogeneous irreversible elementary reaction

CNBr + CH 3 NH 2 CH 3 Br + NCNH 2 with 2.2dm 3

k=

s.mol

rA = kC CNBr C CH 3 NH 2

This reaction is first order in CNBr, first order in CH3NH2 and overall second order.

(3) Heterogeneous catalytic reaction: The following reaction takes place over a solid

catalyst:

32

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