982 23 Optical Spectroscopy and Photochemistry
free radical:CH 3 CH 3
||
Ph 2 C.
O(T 1 )+H—
.
C—OH−→Ph 2.
C–OH+
.
C—OH
||
CH 3 CH 3
(23.6-6)
The next step is the abstraction of a second hydrogen atom from the 2-propanol molecule
by another excited benzophenone molecule, forming another radical and an acetone
molecule (one of the final products):CH 3
|
Ph 2 C.
O(T 1 )+HO—
.
C−→Ph 2.
C–OH+OC(CH 3 ) 2
|
CH 3
(23.6-7)
The final step is combination of two radicals:HO OH
||
2Ph 2.
C–OH−→Ph —C — C— Ph
||
Ph Ph(23.6-8)
The photochemical reaction can be carried out by use of an ultraviolet lamp, but sunlight
contains enough ultraviolet light to produce a significant amount of product in a few
days. The reaction will proceed in a borosilicate glass flask. Borosilicate glass blocks
almost all radiation of wavelength shorter than 300 nm, so the radiation that causes the
reaction to proceed must have wavelengths longer than 300 nm.Exercise 23.9
Calculate the energy per photon and per einstein for radiation of wavelength equal to 300 nm.If naphthalene is placed in the reaction mixture, no reaction takes place. We say
that the reaction isquenched. The explanation is that a rapid intermolecular energy
transfer from an excited benzophenone molecule to a naphthalene molecule returns the
benzophenone molecule to its ground level, before it can react chemically. Naphthalene
has a singlet ground level a singlet (π,π∗) level 4.1 eV above the ground level, and a
triplet (π,π∗) level 2.7 eV above the ground level. A well-obeyed selection rule requires
that in an intermolecular energy transfer the sum of the two electron spin quantum
numbers remains constant. This means that if the benzophenone molecule makes a
transition from a triplet excited level to a singlet ground level, the naphthalene molecule
must make a transition from its singlet ground level to a triplet excited level. If the
benzophenone molecule makes a transition from a singlet excited level the naphthalene
molecule must make a transition to a singlet excited level.
Since the (π,π∗) singlet excited level of naphthalene lies higher than the (n,π∗)
singlet excited level of benzophenone by 0.8 eV, this level cannot be reached by energy
transfer from a benzophenone molecule in its (n,π∗) level. However, the (π,π∗) triplet
excited level of the naphthalene molecule lies lower than the (n,π∗) triplet level of