ElectronicExcitationbyUV/VisSpectroscopy:

Xray:
coreelectron
excitation

UV:
valance
electronic
excitation

IR:
molecular
vibrations

Radiowaves:
Nuclearspinstates
(inamagneticfield)

Thewavelengthandamountoflightthatacompoundabsorbsdependson
itsmolecularstructureandtheconcentrationofthecompoundused.

TheconcentrationdependencefollowsBeersLaw.

A=bc = log I/I0

Where A is absorbance
is the molar absorbtivity with units of L mol-1 cm-1
b is the path length of the sample (typically in cm).
c is the concentration of the compound in solution, expressed in mol L -1

UV Spectrum of Isoprene

=>

- Single bonds are usually too high in excitation energy for most instruments (185 nm)
vacuum UV
most compounds of atmosphere absorb in this range, so difficult to work with.
- Types of electron transitions:
i) , , n electrons

Sigma () single bond electron

Low energy bonding orbital

High energy anti-bonding orbital

Pi () double bond electron

Low energy bonding orbital

High energy anti-bonding orbital

Non-bonding electrons (n): dont take part in any bonds,

neutral energy level.
Example: Formaldehyde

C C

=hv
=hc/

hv

Example:ethyleneabsorbsatmax=165nm=10,000

C O

hv

Thento*transitionisatevenlongerwavelengthsbutisnot
asstrongasto*transitions.Itissaidtobeforbidden.
Example:
Acetone:
n max=188nm;=1860
n max=279nm;=15

C C

135nm

C C

165nm

C O

C O

n 183nm

weak

150nm
n 188nm
n 279nm

weak

188nm

C O

A
279nm

Conjugatedsystems:
C

LUMO

HOMO

Preferred transition is between Highest Occupied Molecular Orbital

(HOMO) and Lowest Unoccupied Molecular Orbital (LUMO).

Additional conjugation (double bonds) lowers the

HOMO-LUMO energy gap:

SimilarstructureshavesimilarUVspectra:
O
O
O

max=238,305nm

max=240,311nm

max=173,192nm

Thevalenceelectronsaretheonlyoneswhoseenergiespermitthemtobe
excitedbynearUV/visibleradiation.
(antibonding)
(antibonding)

n(nonbonding)

(bonding)

Fourtypesoftransitions

*
*
n*
n*

(bonding)
* transition in vacuum UV
n * saturated compounds with non-bonding electrons
~ 150-250 nm
~ 100-3000 ( not strong)
n *, * requires unsaturated functional groups (eq. double bonds)
most commonly used, energy good range for UV/Vis
~ 200 - 700 nm
n * : ~ 10-100
*: ~ 1000 10,000

n*Transitions
Stillratherhighinenergy.between150and250nm.
Notmanymoleculeswithn*transitionsinUV/visregion
max

max

H2O

167

1480

CH3OH

184

150

CH3Cl

173

200

CH3I

258

365

(CH3)2S

229

140

(CH3)2O

184

2520

CH3NH2

215

600

(CH ) N

227

900

n*and*Transitions
MostUV/visspectrainvolvethesetransitions.*are
generallymoreintensethann*.
max

max

C6H13CH=CH2

177

13000*

C5H11CCCH3

178

10000

186

1000

n*

CH3COH

204

41

n*

CH3NO2

280

22

n*

CH3N=NCH3

339

n*

type

O
CH3CCH3
O

Ultraviolet Spectroscopy
200-400 nm photons excite electrons
from a bonding orbital to a *
antibonding orbital.
Conjugated dienes have MOs that are
closer in energy.
A compound that has a longer chain of
conjugated double bonds absorbs light
at a longer wavelength.
=>

Absorption Characteristics of Some Common Chromophores

Chromophore
Alkene

Example

C6H13HC

Solvent

CH2

Alkyne

C5H11C

CH3CCH3
O

Carboxyl

Amido

CH3CH
O
CH3COH
O

Type of
transition

max

n-Heptane

177

13,000

n-Heptane

178
196
225

10,000
2,000
160

*
_
_

n-Hexane

186
280

1,000
16

n*

180
293

Large
12

CH3

Carbonyl

max (nm)

n-Hexane

n*
n*
n*

Ethanol

204

41

n*

Water

214

60

n*

Ethanol

339

n*

CH3CNH2
Azo

H3CN

NCH3

Nitro

CH3NO2

Isooctane

280

22

n*

Nitroso

C4H9NO

Ethyl ether

300
665

100
20

n*

270

12

n*

Nitrate

C2H5ONO2

Dioxane

Most organic spectra are complex

superimposedelectronic and vibration transitions
absorption bands usually broad
detailed theoretical analysis not possible,
effects of solvent & molecular details complicate
comparison

16

- For Compounds with Multiple Chromophores:

If isolated (more than one single bond apart)
- are additive
- constant
CH3CH2CH2CH=CH2

max= 184 max = ~10,000

CH2=CHCH2CH2CH=CH2 max=185 max = ~20,000

If conjugated - shifts to higher s (red shift)

1,3 butadiene:

max= 217 nm ; max= 21,000

1,3,5-hexatriene

max= 258 nm ; max= 35,000

- For Compounds with Multiple Chromophores:

UV Spectral Nomenclature

Blue Shift (Hypsochromic)

Peaks shift to shorter wavelength.

Red Shift (Bathochromic)

Peaks shift to longer wavelength.

Solvent Effects - Intensity

Solventscaninducesignificantchangesintheintensityof
peaks.
HyperchromicIncreaseinabsorptionintensity.
HypochromicDecreaseinabsorptionintensity.
Absorptioncharacteristicsof2methylpyridine
Solvent

max

max

Hexane

260

2000

Chloroform

263

4500

Ethanol

260

4000

Water

260

4000

EthanolHCl(1:1)

262

5200

Solvent effects
-> * transitions leads to more polar
excited state that is more easily stabilized
by polar solvent associations (H-bonds).
The * state is more polar and stabilized
more in polar solvent relative to nonpolar
one, thus in going from nonpolar to polar
solvent there is a red shift or bathochromic
shift (increase in max, decrease in E).

Solvent effects
For n -> * transition, the n state is much more
easily stabilized by polar solvent effects (Hbonds and association), so in going from
nonpolar to polar solvent there is a blue shift
or hypsochromic shift (decrease in max,
increase in E).

n*
methanol

Hypsochromic shift
heptane

Solvent Effects

Auxochrome
Substitutentgroupswhicharenotthemselvesopticallyactiveinthisenergyrange,but
whichdointeractwithotherchromophorestoshiftbothintensityandwavelength.
AbsorptionCharacteristicsofPyridineDerivatives
Derivative

max

max

Pyridine

257

2750

2CH3

262

3560

3CH3

263

3110

4CH3

255

2100

2F

257

3350

2Cl

263

3650

2I

272

400

2OH

230

10000

UVA and UVB

UVA 320nm to 400nm (indirect interaction)
both tans and burns the skin
suppressing the immune system
immediate sunburn reactive oxygen species
UVB 290nm to 320nm (direct interaction)
Skin cancer
Aging
Delayed sunburn

Tanning is based on the control of a complex series of natural

chemical reactions. When exposed to ultraviolet radiation
certain molecules in skin undergo rearrangement. This
rearrangement leads to
formation of Vitamin D from cholesterol,
coloring of skin through the formation of melanins, and
burning or cancer.

Tanning involves the formation of melanin polymers in our skin.

Melanin monomers are already present in the outer layer of the
skin, but in a reduced state. When oxidized upon exposure to
UV, the melanin polymer forms and absorbs light in the visible
and ultraviolet region.

Sun Protection Factor is defined as the ratio of delayed

sunburn on protected skin to unprotected skin, where the
protected skin is covered by 2mg/cm2 of sunscreen.

MED = smallest dose (J/m2) of UVB that

produces a delayed sunburn
SPF 34 should protect you from burning for
thirty-four times the time of unprotected skin.
SPF is based on the physiological response
in the wearer and not based on a direct
comparison of the chemical properties or
dosages of the compounds being used

Active Ingredients

Aminobenzoic acid

15%

Octyl salicylate

5%

Avobenzone

3%

Oxybenzone

6%

Cinoxate

3%

Padimate O

8%

Dioxybenzone

3%

Phenylbenzimidazole sulfonic acid

4%

Homosalate

15%

Sulisobenzone

10%

Menthyl anthranilate

5%

Titanium dioxide

25%

Octocrylene

10%

Trolamine salicylate

12%

Octyl methoxycinnamate

5%

Zinc oxide

25%

(FDA, 1999, p27687)