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Introduction to Reaction Engineering
CHEMICAL KINETICS
 The branch of physical chemistry which deals with
the rate of chemical reactions and the mechanism
through which they occur is called chemical
kinematics.
CLASSIFICATION OF CHEMICAL
REACTION
 (1) Homogeneous and Heterogeneous
reaction
 (2) Catalytic and Non-Catalytic reaction
 (3) Based on Molecularity of Reaction
 (4) Exothermic and Endothermic reaction
 (5) Based on order of reaction
 (6) Reversible and Irreversible reaction
Rate of chemical reaction
 Rate of reaction can be define based on unit volume of
reacting fluid in case of homogeneous system based on
unit mass of solid in case of fluid-solid system and so on.
 select one reaction component for consideration and
define the rate in terms of this component i.
 If the rate of change in number of moles of this
component due to reaction is dNildt, then the rate of
reaction in its various forms can be determioned
Order of a reaction
 The sum of the powers of concentration terms in rate
equation is known as order of reaction.
(or)
 Order of given with respect to all participating reactants
in which case it is called order of reaction.
Consider a reaction mA + nB product
Rate eq (R)=k[A]m[B]n
Order = m + n
Zero Order Reaction
 When the reaction rate is independent of
concentration of the reacting substance, it depends on
the zero power of the reactant and therefore is zero
order reaction.
 The unit of K is concentration time-1
with typical units of mole L-1 s-1.
 Half-life is given by equation;
t1/2 = C0/2k
 The unit of K is concentration time-1
with typical units of mole L-1 s-1.
 Half-life is given by equation;
t1/2 = C0/2k
First order Reaction
 First order reaction consists of one reactant.
A product
R = k[A]1
 Rate constant for first order reaction:
k = 2.303 * log(a/a-x)
t
where, a=initial conc. of A in mol/lit
a-x=change in initial conc. of A in
mol/lit in time interval ’t’
Half Life Time (t1/2)
 Time taken for initial conc. of reactant to become half of
its volume
k= 0.693/t1/2
t1/2=0.693/k
 Units of rate constant for first order reaction: sec-1
Examples of first order reaction
 Thermal decomposition of N2O5
N2O5 N2O3+O2
 Hydrolysis of hydrogen peroxide
H2O2 H2O +1/2O2
 Decomposition of Calcium carbide
CaCO3 CaO + CO2
Second Order Of Reaction
 Second order reaction consists of two reactants.
2A Products
A+B Products
Rate = k[A]2 ; n=2
Rate = k[A][B] ; n=1+1=2
Half Life Time
 Half life time for second order reaction:
t1/2 = 1/a n-1
=1/a as n=2
 Units:
k = mol -1 lit sec -1 (or)
= conc-1. sec -1
Examples Of Second Order Reaction
 Thermal decomposition of Nitrous oxide
2N2O 2N2 +O2
 Decomposition of NO2
2NO 2NO +O 2
 Decomposition of Hydrogen Iodide
2HI H 2 + I2
Third Order Reaction
 Third order reaction includes three reactants
3A Products
r = k [A] 3
A+B+C Products
r = k [A] [B] [C]
2A+B Products
r = k [A]2 [B]
Molecularity of the reaction
 The number of ions or atoms or molecules involve in the
rate determining step or rate limiting step is called
molecularity .
 The molecularity will be only whole number and never
be zero or fraction.
 Molecularity can be determined by reaction mechanism
but it cannot be determined experimentally.
 In no chemical reaction reactants are directly converted
into products in single step, initial reactants are converted
to final products occurred by different internal steps .
These steps are called elementary step reactions .
 The sequential representation of elementary reaction step
in overall chemical reaction is called reaction mechanism.
Example:
A B
Reaction Mechanism:
A 2x
2x 2y
2y B (slow)
 Among all three steps there is a elementary step with
least reaction . This step is called rate determining step or
rate-limiting step.
 Molecularity cannot exceed ‘3’ . If one molecule is
involved in elementary reaction then the reaction is uni-
molecular in nature.
CH2 CH2
2C2H4
CH2 CH2
 In bimolecular reaction the two reactant
molecules(same or different) participate to cause a
chemical change.
2HI H2 + I2
 In tri-molecular there will be collision of three
molecules.
2NO + O2 2NO2
Molecularity
 It is defined as number of
molecules or atoms or
ions participating in rate
determining step.
 It is a theoretical quantity,
which can be determined
through reaction
mechanism.
 It is always whole
number or integer. It can
never be fraction or zero.
Order of reaction
 Order is defined as sum of
powers of concentration
terms in a rate equation.
 Order of reaction can be
determined
experimentally.
 Order of reaction is zero ,
fraction , integer & whole
number.
Intro to reaction enggineering

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Intro to reaction enggineering

  • 2. CHEMICAL KINETICS  The branch of physical chemistry which deals with the rate of chemical reactions and the mechanism through which they occur is called chemical kinematics.
  • 3. CLASSIFICATION OF CHEMICAL REACTION  (1) Homogeneous and Heterogeneous reaction  (2) Catalytic and Non-Catalytic reaction  (3) Based on Molecularity of Reaction  (4) Exothermic and Endothermic reaction  (5) Based on order of reaction  (6) Reversible and Irreversible reaction
  • 4. Rate of chemical reaction  Rate of reaction can be define based on unit volume of reacting fluid in case of homogeneous system based on unit mass of solid in case of fluid-solid system and so on.  select one reaction component for consideration and define the rate in terms of this component i.  If the rate of change in number of moles of this component due to reaction is dNildt, then the rate of reaction in its various forms can be determioned
  • 5. Order of a reaction  The sum of the powers of concentration terms in rate equation is known as order of reaction. (or)  Order of given with respect to all participating reactants in which case it is called order of reaction. Consider a reaction mA + nB product Rate eq (R)=k[A]m[B]n Order = m + n
  • 6. Zero Order Reaction  When the reaction rate is independent of concentration of the reacting substance, it depends on the zero power of the reactant and therefore is zero order reaction.  The unit of K is concentration time-1 with typical units of mole L-1 s-1.  Half-life is given by equation; t1/2 = C0/2k
  • 7.  The unit of K is concentration time-1 with typical units of mole L-1 s-1.  Half-life is given by equation; t1/2 = C0/2k
  • 8. First order Reaction  First order reaction consists of one reactant. A product R = k[A]1  Rate constant for first order reaction: k = 2.303 * log(a/a-x) t where, a=initial conc. of A in mol/lit a-x=change in initial conc. of A in mol/lit in time interval ’t’
  • 9. Half Life Time (t1/2)  Time taken for initial conc. of reactant to become half of its volume k= 0.693/t1/2 t1/2=0.693/k  Units of rate constant for first order reaction: sec-1
  • 10. Examples of first order reaction  Thermal decomposition of N2O5 N2O5 N2O3+O2  Hydrolysis of hydrogen peroxide H2O2 H2O +1/2O2  Decomposition of Calcium carbide CaCO3 CaO + CO2
  • 11. Second Order Of Reaction  Second order reaction consists of two reactants. 2A Products A+B Products Rate = k[A]2 ; n=2 Rate = k[A][B] ; n=1+1=2
  • 12. Half Life Time  Half life time for second order reaction: t1/2 = 1/a n-1 =1/a as n=2  Units: k = mol -1 lit sec -1 (or) = conc-1. sec -1
  • 13. Examples Of Second Order Reaction  Thermal decomposition of Nitrous oxide 2N2O 2N2 +O2  Decomposition of NO2 2NO 2NO +O 2  Decomposition of Hydrogen Iodide 2HI H 2 + I2
  • 14. Third Order Reaction  Third order reaction includes three reactants 3A Products r = k [A] 3 A+B+C Products r = k [A] [B] [C] 2A+B Products r = k [A]2 [B]
  • 15. Molecularity of the reaction  The number of ions or atoms or molecules involve in the rate determining step or rate limiting step is called molecularity .  The molecularity will be only whole number and never be zero or fraction.  Molecularity can be determined by reaction mechanism but it cannot be determined experimentally.
  • 16.  In no chemical reaction reactants are directly converted into products in single step, initial reactants are converted to final products occurred by different internal steps . These steps are called elementary step reactions .  The sequential representation of elementary reaction step in overall chemical reaction is called reaction mechanism.
  • 17. Example: A B Reaction Mechanism: A 2x 2x 2y 2y B (slow)  Among all three steps there is a elementary step with least reaction . This step is called rate determining step or rate-limiting step.
  • 18.  Molecularity cannot exceed ‘3’ . If one molecule is involved in elementary reaction then the reaction is uni- molecular in nature. CH2 CH2 2C2H4 CH2 CH2  In bimolecular reaction the two reactant molecules(same or different) participate to cause a chemical change. 2HI H2 + I2
  • 19.  In tri-molecular there will be collision of three molecules. 2NO + O2 2NO2
  • 20. Molecularity  It is defined as number of molecules or atoms or ions participating in rate determining step.  It is a theoretical quantity, which can be determined through reaction mechanism.  It is always whole number or integer. It can never be fraction or zero. Order of reaction  Order is defined as sum of powers of concentration terms in a rate equation.  Order of reaction can be determined experimentally.  Order of reaction is zero , fraction , integer & whole number.