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CHE244

CHAPTER 1
INTRODUCTION TO CHEMICAL
REACTION ENGINEERING
Prepared by:
ARBANAH MUHAMMAD
arbanah87@gmail.com
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COURSE LEARNING
OUTCOME
1. Classification of reactions
2. Definition of reaction rate
Elementary and nonelementary reactions
Molecularity and order of
reaction

3. Temperature dependent term


of a rate equation
Arrhenius Law
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1.1 CHEMICAL REACTION ENGINEERING (CRE)


Study on the chemical kinetics with the reactor in which the rxns
occur.
Chemical kinetics; tells how long it will take to achieve a specified
level of conversion and what products will be formed.

Chemical reactors are the heart of the majority of industrial chemical


plant.
Operation in the safest and most efficient manner is the key to the
economic success or failure of a chemical plant.

1.1.1 (a) Typical Chemical Process


RAW MATERIAL
SEPARATOR

REACTO
R
SEPARATOR

PRODUCT
/ BY
PRODUCT

1.1.1 (b) Five Aspects Involved in Reactor Design


Mass
Transfer
Heat
Transfer

REACTANT(S)

REACTO
R

Fluid
Mechanics

PRODUCT

Reaction
Kinetics

Thermodynamics
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1.1.2 EXAMPLE OF CRE APPLICATION

Figure 1.1 : Gas-Liquid CSTR (left); batch reactor6(right)

Figure 1.2 : Bench scale reactor


(courtesy of Shell Corp.)

Figure 1.3 : Shell Cat-Cracker (left); All-riser Cracking FCC Unit (right)
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1.1.2 (a) Ethylene Production


Ethylene is used for manufacturing polyethylene - the world's
most widely used plastic
NOVA Chemicals and Dow Chemical at Joffre :

The highest capacity of any ethylene production site in the


world.

Largest single ethane based cracker in the world.

Rxn :
CH CH +H
2

High-temperature 9tubular reactors

1.1.2 (b) SMOG Modeling


Allows to estimate the extent of smog formation ...

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1.1.2 (c) Catalytic Converter


Reduce CO, NO gasses and unburned fuel.

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1.1.2 (d) Large-scale Growth of Stem Cells


The challenge is to grow large quantities of viable cell.

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1.1.2 (e) Pharmacokinetics


CRE can be applied to describe human body-drug interaction

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1.1.2. (f) Fuel Cells System

Fuel Cells

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1.1. 2 (g) Micro-channel Reactors


Compact reactors for compact fuel cells
Production of hazardous chemicals in controlled quantities
Potential application in bio-chemical systems.
Microchannels on a wafer

channel

channel

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1.2 CLASSIFICATION OF REACTIONS


1.2.1 Types of Reactions
a. Homogenous and Heterogeneous
Homogeneous rxn which involve in one phase.
Heterogeneous rxn which involve more than 1 phase
and occurs at the interface between the phases.
Example : CO2 absorption into alkali (gas-liquid); coal
combustion and automobile exhaust purification (gas-solid);
coal liquefaction and oil hydrogenation (gas-liquid-solid).
b. Irreversible and Reversible
Irreversible rxn which proceed in 1 direction and
continues until the reactant are consumed.

Example :

A B C

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Reversible rxn which occurs in backward direction.


(depends on concentration of rxtants and products relative
to the corresponding equilibrium concentration)
Example :

A B C

c. Endothermic and Exothermic


Endothermic rxn that absorbs heat.
Exothermic rxn that releases heat.
d. Molecularity
Molecularity of rxn the no of atoms, ions or molecules involved
(colliding) in a rxn step.
Terms unimolecular, bimolecular and termolecular rxn
involved, one, two or three atoms (or molecules) interacting
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or colliding in any rxn step.


The common example :
i.
Unimolecular : Radioactive decay
ii.

92

238

90Th

234

2 He

Bimolecular : Involving free radicals

Br C2 H 6 HBr C2 H 5
iii.

Termolecular : Almost non-exist

e. Single and Multiple


Single stoichiometric equation and single rate equation
represent the progress for single rxns. Example :

A B C
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More than one kinetic expression to follow the changing


composition of all the rxn components to represent the
progress for single rxns. Multiple rxns may be classified :
i. Series of rxns

A RS
ii. Parallel rxns

R
Z
A
] S

competitive

AR
BS

and

side by side

iii. Complicated scheme : rxn proceeds in parallel with


respect to B, but in series with respect to A, R and S.

A B R
RBS

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1.2.2 Chemical Identity


Chemical species: chemical component or element with a given
identity.
A chemical species is to be reacted when it has lost its chemical
identity.
The identity of a chemical species is determined by the kind, number,
and configuration of that species atoms.
Three ways a chemical species can lose its chemical identity :
a. Decomposition (e.g.
b. Combination (e.g.
c. Isomerization e.g.

CH 3CH 3 H 2 H 2C CH 2
N O 2 NO )
2

CH 3

CH 3

CH 2 C CH 2CH 3 CH 3C CHCH 3
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1.3 DEFINITION OF REACTION


1.3.1 Rate of Reaction
Example of simple reaction :

aA bB cC dD
Rate of rxn ( rA) the no. of moles of A (N) reacting/
disappearing per unit time per unit volume (V) (mol/dm3s).

dC j
1 dN j
rj

V dt
dt

where C = concentration
(N/V = C at const. vol.)

+ if j is a product
if j is a reactant

-rA can describe about how fast a number of moles of one


chemical species rxn to form another species.

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amount of A disappearing
1 dN A
rA

volume time
V dt

mol

m s

For heterogenenous rxn, (-rA) = the no. of moles of A reacting


per unit time per unit mass of catalyst (mol/sg catalyst).
.

1 dN A amount of A disappearing
mol
rA '

W dt
mass of solid time s g catalyst

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1.3.2 Rate Law


Rate equation i.e. rate law ; function of the properties of the
rxtant and rxn conditions (concentration, T or catalyst).
However, it is independent to the type of reactor in which the
rxn is carried out.
Commonly, the rate law is influenced by the composition
(concentration) and the energy of material for homogeneous
rxn.
The definition for energy of material is :
i. Temperature (random kinetic energy of molecules) or
ii. Light intensity within the system (effect the bond energy btw
atoms) or
iii. Magnetic field intensity.
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However, for the heterogeneous rxn, rate law is depend to heat


and mass transfers (surface area of catalyst).
Function of rate law :
concentration

Temperature

rA k T

fn C A , C B

where k = specific reaction rate/ reaction rate constant


Example 1 :
The rate law is :

Example 2 :
The rate law is :

A products
rA kC A

A B P
rA kC C
1
A

1
B
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1.3.3 Order of Reaction


The order of a rxn refers to the powers to which the concentrations
are raised in the kinetic law.
Example :

A B C D

The rate law :

rA kC A CB

= order with respect to rxtant A


= order with respect to rxtant B
n = ( + ) order of rxn
In general :

rA kC C ......C ,
a
A

b
B

d
D

a b ..... d n
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Example :

2 A 3B products

Reaction is 2nd order


with respect to
species A

rA kC C
2
A

3
B

Reaction is 3rd
order with respect
to species B

Thus, the overall order is 2 + 3 = 5


Rate constants, dimension of k for the nth order :

k (unit ) time

concentration

1 n

Exercise :
Unit of k = s-1(mol/dm3)1-n
Zero-order (n = 0) = ________
2nd order (n = 2) = _________

1st order (n = 1) = ________


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1.3.4 Relative Rate of Reaction


If the rate is known with respect to one species, the coefficients
of the balanced chemical equation can be used to find the rates
with respect to the other species.
For rxn :

aA bB cC dD

Note : Taken A species as basis of calculation.

b
c
d
A B C
D
a
a
a
Every mole of A consumed, c/a moles of C produced or formed:

rA rB rC rD


a
b
c d
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Thus, rate of formation of C = c/a x (rate of disappearance of A)


rc = c/a (rA) and so on
Consider the combustion of propane :

C3 H 8 ( g ) 5O2 ( g ) 3CO2 ( g ) 4 H 2O( g )


Compared to the rate with respect to propane :

Rate with respect to oxygen is five times faster

Rate with respect to carbon dioxide is three times faster

Rate with respect to water is four times faster

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Exercise :
The liquid phase rxn :

2 A B 2C
i. Write down the relative of rxn rate.
ii. State the rate law for the above rxn.
iii. What is the rxn rate of A and B if the rate of formation of
C = 4 mol/dm3s.

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1.4 Elementary & Non-Elementary Reaction


The exponents in the rate law are generally
unrelated to the chemical equations coefficients.
Note : Never simply assume the exponents and
coefficients are the same!
The exponents must be determined from the
results of experiments.

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Elementary Process
In general, the rxns mechanism is the series of simple rxns called
elementary processes.
For any rxn shows equal rxn orders of its rxtants with the
stoichiometric coefficients in its stochiometric equation
Thus, the rate law of an elementary process can be written based
on its stoichiometric equation.

Examples :
Stoichometric :
Rate Law :

A 2B C D

rA kC AC

2
B

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Non-elementary Process
There is no direct correspondence between stoichiometry and rate
stoichiometry does not match its kinetics.
Examples :
Stoichometric :

H 2 Br2 2HBr

Rate Law :

rHBr

k1 H 2 Br2

1/ 2

k 2 HBr / Br2

This nonmatch show a multisteps rxn model have to be


developed to explains the kinetics.
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In order to explain the non-elementary rxn, assume the sequence of


elementary rxn is occurred but we can not measure or observe
the intermediates.

Thus, we need to observe only the initial rxtants and final products
appear in a single rxn formed they only present in very minute
quantities.

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1.4 TEMPERATURE DEPENDENT TERM OF A RATE


EQUATION ARRHENIUSS LAW
1.4.1 Parameters Affect
For many rxns, the rate expression can be written as a
product of a temperature-dependent term and a composition
dependent term :

rA

fn1 (T ) fn2 (C )

rA k (T ) fn2 (C )
k : determination of
activation energy

Determination of
rxn order
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Rate constant (k) is strongly depend on temperature.


Thus, for the temperature-dependent term, k , the correlated
equations are:

rA k (T ) C A kC Ae

Ea

RT

Temperature
dependent
term

1.4.2 Arrhenius Law


In general, the Arrhenius equation shows "the dependence of
the rate constant, k, of chemical rxns on the temperature T
and Ea :
E

k (T ) A e

RT

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where: A = pre-exponent/ frequency factor

Ea = activation energy, J/mol or cal/mol


R = gas constant = 8.314 J/molK = 1.987 cal/molK
T = absolute temperature, K
The equation known as Arrhenius Law molecules need energy to
distort/ stretch their bonds so that they break them and thus form
new bonds.

k Ae

RT

ln k ln A E

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RT

The Arrhenius equation can be put in standard slope-intercept


form by taking the natural logarithm.
A plot of ln k versus (1/T) gives a straight line with slope
= Ea/RT

ln k ln A Ea / RT

or

ln k ln A ( Ea / R) (1 / T )

y b

Figure 1.4 : Arrhenius Plot


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Rxn with high Ea are very temperature sensitive and rxn with
low Ea are relatively temperature-insensitive.
For any given rxn, the temperature more sensitive at low
temperature than at very high temperature.
Temp sensitive

Temp insensitive

Figure 1.5 : Temperature sensitive and temperature-insensitive for Arrhenius


Plot
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The Ea can be related to the rate constant at two temperatures :

E 1 1
k (T ) ko (T ) exp

R To T

k E 1 1
ln

ko R To T

As a rule of thumb, a 10C rise in temperature causes a rxn rate


to double.
However, this is true only for a specific combination of
activation energy and temperature.
For example, if the Ea is 53.6 kJ/mol, the rate will double only if
the temperature is raised from 300 K to 310 K.

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THIS IS THE END OF


CHAPTER 1
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