Module 1

Introduction:
The rate of chemical reaction tells us how fast a number of moles of one chemical species are being
consumed to form another chemical species.Achemical reaction takes place by decomposition,
combination or by change in configuration of molecules.

1. Decomposition CH3CH3 H2 + H2C=CH2

2. Combination N2 + O2 2 NO

3. Isomerization C2H5CH=CH2 CH2=C(CH3)2

The rate of a chemical reaction refers to the reactant consumption or the product formation per unit
time. If the rate of change in number of moles of component due to reaction is then,

i.e., the number of moles of component i formed per unit time per unit volume (mol/dm3s).

The rate of a reaction (mol/litre.s) can be expressed as eitherthe rate of disappearance (-rA)or as the
rate of formation (generation), rA.

Consider a reaction A B

-rA = the rate of a disappearance of species A

= moles of A consumed per unit volume (mass) per unit time
rB = the rate of formation of species B

NOTE:“minus” sign denotes consumption or disappearance

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EXAMPLE: Consider a reaction, AB.If Species B is being formed at a rate of 0.2 moles per decimeter
cubed per second, i.e., 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

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For a catalytic reaction we refer to –rA’ , which is the rate of disappearance of species A on a per mass of
catalyst basis. (mol/gcat.s)

For constant volume system,

where, Ci is the concentration of species i in reaction mixture

Note: Reaction rate (intrinsic) is-

(i) function of temperature and reactant concentrations.
(ii) independent of reactor type.
(iii) described by a kinetic expression or rate law.

Note:rA = dCA/dt is valid for only a constant volume batch reactor system with perfect mixing.

Relative rates of reaction (stoichiometric coefficients)

For a reaction vAA + vBB = vCC + vDD

On a “per mole of A basis”…..i.e. assume A is the limiting reactant.The reactant consumption or the
d[A]
product formation per unit time can be written as, rate based on reactant A
dt
d[B] d[C] d[D]
similarly we can write , rate or rate or rate
dt dt dt

Are these the same rate?

Depending on the stoichiometry coefficients. The equivalent rate is:

1 d [A] 1 d [B] 1 d [C] 1 d [D]

rate
v A dt vB dt vC dt vD dt

Then the reaction stoichiometry is:

e.g. N2 + 3H2 = 2NH3

1 d[N 2 ] 1 d[H 2 ] 1 d[NH3 ]

rate
1 dt 3 dt 2 dt
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EXAMPLE: For an elementary reaction,

(a) Rate of appearance of C is equal to rate of disappearance of A

(b) Rate of disappearance of A is equal to rate of disappearance of B
(c) Rate of appearance of C is equal to rate of disappearance of B
(d) Rate of appearance of C is 3 times rate of disappearance of A

Solution:

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Factors affecting rate of reaction: The Rate Law:

1. The nature of species involved in the reaction
2. Concentration of species
3. Temperature
4. Catalytic activity
5. Nature of contact of reactants
6. Wavelength of incident radiation

Rate law and Reaction order:

The basis of calculation is always the limiting reactant.

The rate of disappearance of A, -rA, depends on temperature and composition.

The rate of reaction can be written as the product of a reaction rate constant kA, and a function of the
concentrations of the various species involved in the reaction:

-rA= [kA (T)] [f (CA, CB, …)]

The algebraic equation that relates –rA, to the species concentrations is called the kinetic expression or
rate law. The specific rate of reaction (also called the rate constant) is kA.
Power Law or Elementary Rate Law

Consider the general equation

Reaction order with respect to a specific component (either reactant or product) is the power to which
the concentration of that component is raised in the kinetic equation.
d[i]
If rate equation is ri k[A] [B] [C] [D]
dt
Then, order w.r.t. A is a, the order w.r.t. B is b, the order w.r.t. C is l, etc….

Overall Reaction order- is the sum of orders of all reactants & products

Note: 1) A reaction order do not have to be an integral, it can be a fraction.

e.g. C4H10+3.5O2=C4H2O3+4H2O
70000 0.36 0.98 0.5 0.11
rnB 3.4 104 exp( ) PnB PO2 PH2O PMA
RT
2) Some rate eqns. are very complicated - we do not use the term ‘reaction order’.

e.g. CO+H2O=CO2+H2
kPH 2O
r
1 K 2 PH 2O / PH 2

The units of –rA, are always in terms of concentration per unit time while the units of the specific
reaction rate, kA, will vary with the order of the reaction.

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EXAMPLE: Rate expression of reaction is,

If the concentration is to be expressed in mol/l and time in hours, the value of rate constant would be:
Solution:

1 L = 10 cm3 and 1hour = 60 min

EXAMPLE: The rate of reaction for a gas phase reaction is expressed as:

The units of rate constant are:

k=

………………………………………………………………………………………………………………………………………………………………….

Types of reactions:
1. A homogeneous reaction is one which takes place in only one phase. i.e. all the reacting material
and products and catalyst (if any) will be present in similar phases.
A heterogeneous reaction is one which involves more than one phases.

2. Catalytic reactions are those reaction which involves use of catalyst to enhance the rate of
reaction.
Non-catalytic reactions are those reaction which does not involve the use of catalyst.
 3. The reaction may be classified based upon the molecularity of reaction i.e. based upon the
number of molecules that takes part in chemical reaction as unimolecular, bimolecular and
trimolecular reaction.

Unimolecular A Pr od . rA kC A
Bimolecular 2A Pr od . rA kC A2
Bimolecular A B Pr od . rA kC ACB
Trimolecular 3A Pr od . rA kC A3
Trimolecular 2A B Pr od . rA kC A2CB
Trimolecular A B C Pr od. rA kCACBCC

4. The reaction may be classified as exothermic and endothermic reaction.

Exothermic reaction is one in which heat is evolved.
Endothermic reaction is the one in which heat is absorbed.

5. The reaction may be classified as reversible and irreversible reaction.

Reversible reaction are those in which forward and reverse reaction takes place simultaneously.
Irreversible reaction are those which can proceed only in one direction.

6. The reaction may be classified as first order, second order and third order reaction.

Single and multiple reaction:

In single reaction, a single rate equation is chosen to represent the progress of a reaction. Whereas in
multiple reaction, more than one kinetic expression is needed to follow the changes in the
concentration of all the reaction component.Multiple reaction may be classified as:
Elementary and non-elementary reactions:
Consider a single reaction A+ B--- > C

According to rate law, rate of disappearance of A,

Such reaction in which the rate equation correspond to the stoichiometric equation are called
elementary reactions.

When there is no direct corresponding rate and stoichiometry, then the reaction is called non-
elementary reaction. The best example is

H2 + Br2 → 2HBr
which has rate expression,

NOTE:A reaction follows an elementary rate law if and only if the stoichiometric coefficients are
the same as the individual reaction order of each species.

Reversible Reaction

The net rate of formation of any species is equal to its rate of formation in the forward reaction
plus its rate of formation in the reverse reaction: A + B C

ratenet = rateforward + ratereverse

At equilibrium, ratenet 0 and the rate law must reduce to an equation that is
thermodynamically consistent with the equilibrium constant for the reaction.

…………………………………………………………………………………………………………………………………………………….
EXAMPLE:

Or

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Molecularity and order of reaction:
The term molecularity refers to the number of atoms, ions or molecules involved in the rate limiting step
of the reaction.

Consider a reaction,

Then rate expression,

Where a,b,…..d are not necessarily related to the stoichiometric coefficient .

Then the power to which concentration are raised is the order of reaction. Hence the reaction is-
ath order with respect to A
bth order with respect to B
cth order with respect to C

Note: Since the order refers to the empirically found rate expression, it may not be an integer and may
have a fractional value.But, the molecularity of reactionmust be an integer as it refers to mechanism of
reaction and applies only to elementary reaction.

NOTE:No elementary reaction with molecularity greater than three have been found.

Rate constant:
The rate constant of chemical reaction is a measure of the rate of reaction when all the reactants are at
unit concentration.Forany reaction,

-rA = kCA

If concentration are equal to unity, then -rA = kwhere k is the rate constant.

NOTE: k is the reaction rate constant

Independent of reactant / product concentration

Dependent on the reaction temperature. It increases with temperature.
The unit of k depends on the unit of all other terms in the rate equation
Let,

And as we know the units of ( ) = mol/l sec

So,

where n is the order of reaction.

………………………………………………………………………………………………………………………………………………………………….

Example: (mol g-1 h-1), and Pi is the partial pressure in bar

Then, unit of k will be:

………………………………………………………………………………………………………………………………………………………………….
Examples of reaction rate law: