Dr.

Usama El-Ayaan

Dr. Usama El-Ayaan

Dr. Usama El-Ayaan





(5s , 5p ) +, 4f $ & # " #

Crystal/Ligand field effects in lanthanide 4f orbitals are virtually insignificant

4f electrons are well shielded from external charge by 5s2 & 5p6 shells
f-f absorption bands are very sharp (useful fingerprinting and quantitation of LnIII)
optical spectra are virtually independent of environment (like, solvent,.
Dr. Usama ElEl-Ayaan

Absorption by f electrons
4f and 5f metals absorb because of f electron excitation

" #
f
(5s and 5p) $ % &
,- $ +
' *

. .

-
# / .
Spectra have sharp, well
defined absorption peaks.

Dr. Usama El-Ayaan

Absorption by d electrons
Most period 4 & 5 transition metals have at least one species (cation)
that absorbs radiation in the visible region.
Absorption is due to the excitation of the outer shell d electrons.
The d orbitals are partially filled and the d electrons are highly
influenced by external forces since they are in the outermost shell.
Transition metals have broad band absorption spectra and max is
affected by solvent and ligands.

Dr. Usama El-Ayaan

Dr. Usama El-Ayaan

Dr. Usama El-Ayaan


Dr. Usama El-Ayaan

 -8 complexes
,

/
&2 3 . - 2 3 2 5 .

, 6 3
3 8 . , 3

Dr. Usama ElEl-Ayaan

 , & 2 3

Oxalate

Citrate

acetylacetone
Dr. Usama ElEl-Ayaan

Tartrate

 , :
EDTA

ethylenediaminetetraacetic acid
,

. 6

CN = 6

= "

El-Ayaan
Dr. Usama
El#8 : 6 2

7,8 and 9

CN = 8

: 2

CN = 7 2

Dr. Usama ElEl-Ayaan

CN = 9

[Ln(H2O)9]3+

Dr. Usama ElEl-Ayaan

, 6 ( 10,12) , 2
SO42- NO3-

[Ce (NO3)6]3CN = 12

[Ce (NO3)5]2

Dr. Usama ElEl-Ayaan

CN = 10

#& Ln3+

,
(1.03
)03--0.86
) (Cr3+ = 0.615 , Fe3+ = 0.55
.

" !
$ & ' 4f
ligands
) .
Dr. Usama ElEl-Ayaan

) (bonding