Today’s Important Concepts

Free Radical Halogenation of Alkanes

Relative stability of Free Radicals
Reactivity-Selectivity Principle
Hammond’s Postulate

For Weds 2/25 Read 5.1-5.7-Alkenes

Problems 5.1-23, 25-37

 




The
Hammond
Postulate

 The
Hammond
Postulate

•  In
an
endothermic
reac)on,
the
transi)on
state
resembles
the
products
more
than
the
reactants.
Any
factor
that
stabilizes
the

product
also
stabilizes
the
transi)on
state.
Thus,
lowering
the
energy
of
the
transi)on
state
decreases
Ea,
which
increases
reac)on

rate.





















The
Hammond
Postulate

•  In
the
case
of
an
exothermic
reac)on,
the
transi)on
state
resembles
the
reactants
more
than
the
products.
Thus,
lowering
the

energy
of
the
products
has
less
effect
on
the
energy
of
the
transi)on
state
than
in
an
endothermic
reac)on.


 Alkyl
Halides
and
SN1
Subs)tu)on

The
Hammond
Postulate

• The
Hammond
postulate
es)mates
the
rela)ve
energy
of
transi)on
states,

and
thus
it
can
be
used
to
predict
the
rela)ve
rates
of
two
reac)ons.

• According
to
the
Hammond
postulate,
the
stability
of
the
carboca)on

determines
the
rate
of
its
forma)on.

Page 161 Eqn. 5
Page 176 Eqn. 1
Page 176 Eqn. 2
Page 176 Eqn. 3
Page 168 Eqn. 2
Page 168 Eqn. 1
Page 168 Eqn. 3
Page 170
Page 171
Page 172
Page 164
Fig. 4.18
Page 166 Eqn. 1
Page 170 Eqn. 1
Page 170 Eqn. 2
Page 170 Eqn. 3
Page 171 Eqn. 1
Page 171 Eqn. 2
Page 172 Eqn. 1
Tab. 4.3