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

Beer's Law:
A = bc = log T = log

I
I
= log 0
I0
I

Absorbance is additive
A total = A1 + A2 ...
= 1bc1 + 2 bc 2 ...
in a 2 component mixture
A1 = 1,1 b c1 + 2, 1 b c2
A 2 = 1,2 b c1 + 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 = log T 1 = 1 bc
I
= log 0
I
I 1 = I 0 1 10

1 bc

I 2 = I 0 2 10

bc
2

I
0 1 + I 0 2

A =
I 1 + I 2

I
+
I
0

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

A = log I 0 1 + I 0 2 log I 0 1 10

CEM 333 page 4.2

1 bc

+ I 0 2 10

2 bc

 non-linear calibration curve (Fig 13-4, 13-5)

CEM 333 page 4.3

Typical UV-Vis Spectrophotometers:

includes selection

(Fig 13-12)

(a) single beam (SB) (b) double-beam (DB)-in-space (c) doublebeam-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:

excitation

relaxation

M + h
M*
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
= sA + sB
* = sA sB
= pA + p B
* = pA p B

Bonding molecular orbital

Antibonding * molecular orbital
Bonding molecular orbital
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

CH2=CHCH2CH2CH=CH2 max =185 nm
CH2=CHCH=CH2 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

Cr(III)

6Cl-

6H20

6NH3

3en

6CN-

736

573

462

456

380

I-<Br-<Cl-<F-<OH-<C2O42-~H2O<SCN-<NH3<en<NO2-<CNvis

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