Rate laws

Yuana Elly. A., S.T., M.Sc

September, 104
Rate law and Reaction order
The order of a reaction refers to the
powers to which the concentrations are
raised in the kinetic rate law.
the reaction in the above equation is α order
with respect to reactant A. and β order
with respect to reactant B.
The overall order of the reaction, n, is
n=α+β
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.
 Consider a reaction involving only one reactant, such as
A Products
 with a reaction order n. The units of the specific reaction
rate constant k are
(concentration)1 n
k
time
 Then for
 Rate equation
Single and multiple reaction :
Single reaction : A  B or A + B  C + D
Multiple reaction :
 Series reaction : A  B  C
 Parallel reaction : A  B
AC
Elementary and non elementary reactions :
Elementary reactions : rate equation corresponds
to the stoichiometric reaction
A + 2B  C, -rA = k. CA. CB2. where k : rate constant
Non elementary reaction : rate equation isn’t
related to the stoichiometric reaction
2A  3B, -rA= k.C2A/CB, where k : rate constant
Elementary rate laws
For an elementary reaction such as
the bimoIecuIar reaction between oxygen
and methanol

The reaction is first order in molecular

oxygen and first order in methanol
therefore. we say both the reaction and the
rate law are elementary.
 Types of Elementary Reaction
Unimolecular
O*  O + O
Rate = k. [O*]
Bimolecular
NO(g) + O3(g)  NO2(g) + O2(g)
Rate = k. [NO]. [O3]
Termolecular
O + O2 + M  O3 + M
Rate = k. [O]. [O2]. [M]
Termolecular reactions are low probability
reactions; require three species to come together
simultaneously
 2H2O2(aq)  2 H2O(l) + O2(g)
Experimental rate law: Rate = k [H2O2][I-]

(i) H2O2 + I-  H2O + OI- slow

(ii) OI- + H2O2  H2O + O2 + I- fast

Rate depends on the slow, rate-determining step,

(i)

Here, OI- is the intermediate species

2NO2 + F2  2 NO2F

Experimental rate expression

rate = kobs [NO2] [F2]

Possible mechanism which fits the experimental

observation
NO2 + F2  NO2F + F slow
NO2 + F  NO2F fast

First step: rate = k1 [NO2] [F2] rate determining step

Second step: rate = k2 [NO2] [F]

The rate of the first reaction determines the rate of

the overall reaction
Elementary Rate Laws
 There are many reactions where the stoichiometric
coefficients in the reaction are identical to the reaction
orders but the reactions are not elementary owing to
such things as path-ways involving active
intermediates and series reactions. For these reactions
that are not elementary but whose stoichiometric
coefficients are identical to the reaction orders in the
rate law, we say the reaction follows an elementary
rate law.

 For example, the oxidation reaction of nitric oxide

2NO + O2 2NO2
The reaction is not elementary but follows
the elementary rate law
 Non elementary Rate
Laws
A large number of both homogeneous and
heterogeneous reactions do not follow simple
rate laws.

Examples of Homogeneous Reactions

CO +Cl2 COCl2

This reaction is first order with respect to

carbon monoxide, three-halves order
with respect to chlorine. and five-halves order
overall
Non elementary Rate
Laws
Example of Heterogeneous Reactions
In many pas-solid catalyzed reactions. It
historically has been the practice to
write the rate law in terms of partial
pressures rather than concentrations.
C6H5CH3+ H2 C6H6 +CH4
Remember