UV-Vis (Absorption) Spectrometry (Chapters 13, 14) Beer's Law: A = bc = log T = log 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 I I = log 0 I0 I

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 bc
2

I 2 = I 0 2 10

I + I0 2 0 1 A = I 1 + I 2

I 0 1 + I 0 2 = bc bc I 10 1 + I 0 2 10 2 0 1 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) 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: M + h M* M + h / heat How probable? ranges 0 to ~100,000 L/molcm "forbidden" 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 "allowed"
excitation relaxation

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 * n* E large (<150 nm) =10-10,000 L/molcm (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 6ClCr(III) 736 6H20 573 6NH3 462 3en 456 6CN380

I-<Br-<Cl-<F-<OH-<C2O42-~H2O<SCN-<NH3<en<NO2-<CNvis "Spectrochemical Series" UV

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