Inorganic Reaction Mechanisms

By
Prof. Laila Hamdan Abdel-Rahman
 Prof. Ramadan M. Ramadan
http://rmramadan-notes.pbworks.com
 Introduction
• Most chemical reactions occur by mechanisms that involve more than
one step.
• As a result, the rate law can not be directly deduced from the
stoichiometry of a balanced chemical equation.
• Only elementary reactions(those which occur in one step) can give the rate law.
• Among the steps in a multi-step reaction, there is always one that is slowest
compared to the rest.
• This slowest step limits the overall reaction rate and is called the rate-
determining step.
• The rate-determining step determines the rate law for the overall reaction.
Example 1
NO2 (g) + CO (g) ====== NO (g) + CO2 (g)
• This reaction is found to be second order with respect to [NO2]
and zero order with respect to [CO]:
Rate = k [NO2]2
• The following mechanism has been proposed:
• Step 1: NO2 (g) + NO2 (g) ===== NO3 (g) + NO (g) slow
• Step 2: NO3 (g) + CO (g) ===== NO2 (g) + CO2 (g) fast
• Overall: NO2 (g) + CO (g) ===== NO (g) + CO2 (g)
• Since Step1 is the slowest step, it determines the rate of the
overall reaction.
 Example 2

2 NO (g) + O2 (g) ===== 2 NO2 (g)

• This reaction proceeds with the following observed rate law:
Rate = kobs [NO]2 [O2]
• One possible mechanism is a one-step reaction between two
molecules of nitrogen oxide and a molecule of oxygen.
• This mechanism is very unlikely since three way collisions are
highly improbable.
• An alternative mechanism is provided by the following:
• Both steps are bimolecular, which are more likely to happen than a three way collision.
• The slow step determines the overall reaction rate:
Rate = k2 [N2O2] [O2]
• This equation is a sort of useless since it contains a term that does not correspond to
either any of the reactants or the product.
• "A rate law should only consist of concentrations of reactants and/or products, no
intermediates".
• Since the intermediate, dinitrogen dioxide, reacts slowly with oxygen, the reverse
reaction of Step 1 is possible.
• Assume that Step 1 will reach a dynamic equilibrium, which will lead to a constant
concentration of dinitrogen dioxide.
• thus, the forward and reverse rates of Step 1 are equal:
 Definitions

• a) "Lability" and "inert" are kinetic terms.

• b) "Stable" and "unstable" are thermodynamic
statements.
• c) "Intimate" mechanism refers to the details of the
mechanism on the molecular scale.
 General Substitution Reactions of Octahedral Complexes
1- The Dissociative Mechanism (D Mechanism)
• This type can be compared with the SN1 type, but it differs in the
law of the observed reaction rate.
• It is supposed that the five coordinate intermediate in such
mechanism is surviving a period of time in presence of the
outgoing ligand, L, the incoming ligand, L', and the solvent
molecules.
• In this case the rate of the reaction does not depend on the
concentration of the incoming ligand where there is a complete
cleavage of the M-L before the formation of M-L' bond.
• Thus, by considering the following steps:
 2- The Associative Mechanism (A Mechanism)
• This type of mechanism is characterized by a complete formation
of a seven coordinate intermediate, ML6L'.
• This is followed by a dissociation step to form the product
compound.
 3- The Dissociative Interchange Mechanism (Id Mechanism)
• In this mechanism, the transition state involves large elongation
of one of the M-L bonds without complete rupture along with
slight reaction with the incoming ligan(L').d
• This primary reaction of the incoming ligand and the octahedral
complex gives some sort of weak intermediate ML6.L' where the
L' enters the first coordination sphere at the same time the
outgoing ligand leaves.
• So, the mechanism of reaction can be represented as:
 4- The Associative Interchange Mechanism
(Ia Mechanism)
• Here, exchange of ligands is occurred between
the inner sphere and the followed one.
• In this case, the reaction between the metal ion
and L' is stronger in the transition state, i.e., the
formation of bond is important in the activated
complex.