UV-Vis (Absorption) Spectrometry (Chapters 13, 14)

Beer's Law:
A = bc = logT = log
I
I
0
= log
I
0
I
Absorbance is additive
A
total
= A
1
+ A
2
...
=
1
bc
1
+
2
bc
2
...
in a 2 component mixture
A
1
=
1,1
b c
1
+
2, 1
b c
2
A
2
=
1,2
b c
1
+
2,2
b c
2
Limitations of Beer's Law (pp 303-311):
(1) Chemical effects - analyte associates, dissociates or
reacts to give molecule with different
Fig 13-3
CEM 333 page 4.1
(2) Physical effects - stray light, polychromatic radiation
or noise
A

1
= logT

1
=

1
bc
= log
I
0
I

1
I

1
= I
0
1
10

1
bc
I

2
= I
0
2
10

2
bc
A

=
I
0
1
+ I
0
2
I

1
+ I

2








=
I
0
1
+ I
0
2
I
0
1
10

1
bc
+ I
0
2
10

2
bc










A

= log I
0
1
+ I
0
2
( )
log I
0
1
10

1
bc
+ I
0
2
10

2
bc
( )
CEM 333 page 4.2
non-linear calibration curve (Fig 13-4, 13-5)
CEM 333 page 4.3
Typical UV-Vis Spectrophotometers:
(Fig 13-12) includes selection
(a) single beam (SB) (b) double-beam (DB)-in-space (c) double-
beam-in-time
CEM 333 page 4.4
Multichannel Spectrophotometer
No monochromator, but disperses transmitted light and measures "all
wavelengths at once" (Fig 13-13)
No scanning - simple and fast
More expensive
Limited resolution
CEM 333 page 4.5
Applications of UV-Vis Spectrometry:
M+ h
excitation
M
*
relaxation
M+ h / heat
How probable?
ranges 0 to ~100,000 L/molcm
"forbidden" "allowed"
electronic transition
Which electrons get excited?
In UV-Vis, photon provides enough energy to move outer valence
(bonding) electrons
Organic molecules

=
s
A
+
s
B
Bonding molecular orbital

*
=
s
A

s
B
Antibonding
*
molecular orbital

=
p
A
+
p
B
Bonding molecular orbital

*
=
p
A

p
B
Antibonding
*
molecular orbital
Fig 14-1
CEM 333 page 4.6
, (bonding) and n (non-bonding) electrons
Fig 14-2
Arrange in terms of energy:
Fig 14-3
* E large (<150 nm) =10-10,000 L/molcm
n* (halogens, N, O, S) E smaller (=150-250 nm)
=200-2000 L/molcm
* n* E small (=200-700 nm) =10-10,000 L/molcm
Ideal for UV-Vis spectrometry of organic chromophore
CEM 333 page 4.7
Red shift of
max
with increasing conjugation
CH
2
=CHCH
2
CH
2
CH=CH
2

max
=185 nm
CH
2
=CHCH=CH
2

max
=217 nm
Red shift of
max
with # of rings
Benzene
max
=204 nm
Naphthalene
max
=286 nm
Blurred with solvent
Fig 14-5
CEM 333 page 4.8
Inorganic Ions
Most transition metal ions are colored (absorb in UV-vis) due to
dd electronic transitions (Fig 14-7)
Remember:
Solution absorbs red appears blue-green
Solution absorbs blue-green appears red
CEM 333 page 4.9
Ligands cause different interactions with d electrons (Fig 14-8, 14-9)
- ligand field splitting
CEM 333 page 4.10
Ligand Field Strengths:

max
for complex (nm)
Increasing Ligand Field Strength
6Cl
-
6H
2
0 6NH
3
3en 6CN
-
Cr(III) 736 573 462 456 380
I
-
<Br
-
<Cl
-
<F
-
<OH
-
<C
2
O
4
2-
~H
2
O<SCN
-
<NH
3
<en<NO
2
-
<CN
-
vis UV
"Spectrochemical Series"
CEM 333 page 4.11
Solvent Effects:
(i) Solvent transparency in UV (Table 14-6)
(ii) Polar solvents "blur" vibrational features more than nonpolar
(iii) Polar solvents more likely to shift absorption maxima
Shifts of
max
with solvent polarity
n* hypsochromic/blue shift
* bathochromic/red shift
CEM 333 page 4.12
Fig 14-12
Solvent effects mean UV-Vis not reliable for qualitative but
excellent for quatitative analysis.
CEM 333 page 4.13