2.1.

3 Intermediate Stability
Intermediate is a molecular entity that is formed from the reactants (or preceding
intermediates) and reacts further to give the directly observed products of a chemical reaction. In
other words, it is a reacting species which is no longer a starting material or reactant, and has not
yet become product. When the necessary conditions of the reaction no longer prevail, these
intermediates react further and no longer remain in the reaction mixture. Hence, they do not
appear in the final products of the reaction.
Intermediates are similar to transition states in that they allow the mechanism to be
defined or theorized, but they differ from each other, although the differences are subtle.
Intermediates have discrete lifetimes be it a few nanoseconds or many days, whereas transition
states last for just one bond vibration cycle. Besides that, intermediates are part of a stepwise
change and can occasionally be directly observed to exist while transition states are usually part
of a coordinated change and not directly observable.
Intermediate may be unstable molecules, in which case they are called reaction
intermediate, or highly stable molecules. Many of them are short-lived and highly reactive, thus
having a low concentration in the reaction mixture. Reaction intermediates are often free radicals
or unstable ions such as carbocations.
The most common intermediate in organic reactions is carbocations. Since carbocation is
electron-deficient and therefore unstable, it will be stabilized by nearby electron-donating group.
The stability of carbocations increase from primary to tertiary due to three factors, which are
neighbouring carbon atoms, neighbouring carbon-carbon multiple bonds and neighbouring atoms
with lone pairs.

In the first factor which is neighbouring carbon atoms, carbons or alkyl groups in
particular are considered as electron-releasing groups through inductive effect. The inductive
effect means that the carbon that is connected to the hydrogen will be electron-rich since it is
more electronegativity than hydrogen, and can donate some of those electrons to the
neighbouring carbocation. This method can also be explained through hyperconjugation, a
process which invokes stabilization through donation of the electrons in C-H sigma bonds to the
empty p-orbital of the carbocation. Therefore, the more alkyl groups attached to carbocation, the
more stable the carbocation is.
The second factor is neighbouring carbon-carbon multiple bond. Carbocations adjacent to
another carbon-carbon double or triple bond have special stability because overlap between the
empty p orbital of the carbocation with the p orbitals of the bond allows for charge to be shared
between multiple atoms. This effect is called delocalization and is a major stabilizing influence.
The last factor is neighbouring atoms with lone pairs. The neighbouring atom will
donates a pair of electrons to the electron-poor carbocation which results in formation of double
bond and the charge will move to the atom donating the electron pair. This process often goes by
the name of donation. The strength of this effect varies with basicity, so nitrogen and oxygen
are the most powerful donors. Even halogens can help to stabilize carbocations through
donation of a lone pair.
In the reaction of hydrohalogenation of alkenes and dehydrohalogenation of haloalkanes,
the reactants will become intermediates before turning into the final products, which are
haloalkane and alkene respectively. Therefore, the stability of the intermediates, which are

carbocations in these reactions, plays an important part as they affect the production of the final
product.
The stability of carbocation increase from primary to secondary, and finally, to tertiary. In
general, the pathway leading to more stable intermediate will be of lower energy; hence it will be
the preferred pathway. The more stable the carbocation, the lower the activation energy of the
reaction which will lead to a more stable transition state. The increased stability of the ratelimiting transition state in turn will increases the rate of reaction and substantially increase the
number of products form which is haloalkane for the reaction of hydrohalogenation of alkenes
and dehydrohalogenation of haloalkanes. Therefore, the effect of intermediate stability on the
final product of hydrohalogenation of alkenes and dehydrohalogenation of haloalkanes is
increasing the amount of products formed.