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Chapter 2

Ultraviolet and Visible

Absorption Spectroscopy (UV-Vis)

At room temperature, most of the atoms, molecules and electrons are in the lowest energy orbital called ground state.

The electron of atom (molecule) at ground state can

absorb proton and transit to higher energy orbital called excited state.

Atom or molecule can absorb the radiation only when the energy of proton is equal to the energy difference of the

two orbitals

  • 2.1 Basic principles of UV-vis

Ultraviolet-visible spectroscopy corresponds to excitations of outer shell

electron between the energy levels that correspond to the molecular orbital of the

systems.

The band spectrum of molecule due to vibrational and rotational levels

Comparing: Atomic spectrum

  • 2.2 Molecular orbitals and

electronic transition

While two atoms form chemical bond, their atomic orbital combine together to form molecular orbital. Bonding orbital and antibonding orbital Bonding orbital energy level is always lower than that of the original atomic orbital Antibonding orbital energy - higher  s , p orbitals and h electrons

Types of Electronic

Transitions

  • 1. Transitions involving p, s, and n electrons

  • 2. Transitions involving charge-transfer electrons

  • 3. Transitions involving d and f electrons (not covered in this Unit)

Absorbing species containing p, s, and n electrons

Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain functional groups (chromophores) that contain valence electrons of low excitation energy. The

spectrum of a molecule containing these

chromophores is complex. This is because the superposition of rotational and vibrational transitions on the electronic transitions gives a

combination of overlapping lines. This appears as a continuous absorption band.

s - s * Transitions

An electron in a bonding s orbital is excited to the corresponding antibonding

orbital. The energy required is large. For example, methane (which has only C-H bonds, and can only undergo s - s transitions) shows an absorbance maximum at 125 nm. Absorption maxima due to s - s * transitions are not seen in typical UV-Vis. spectra (200 - 700 nm)

*

n - s * Transitions

Saturated compounds containing atoms with lone pairs (non-bonding electrons) are

capable of n - s * transitions. These transitions usually need less energy than s - s * transitions. They can be initiated by light whose wavelength is in the range 150 - 250 nm. The number of organic functional groups with n - s * peaks in the UV region is small.

n - p * and p - p * Transitions

Most absorption spectroscopy of organic compounds is based on transitions of n or p electrons to the p * excited state. This is because the absorption peaks for these transitions fall in an experimentally convenient region of the spectrum (200 - 700 nm). These transitions need an unsaturated group in the molecule to provide the p electrons.

n - p * and p - p * Transitions

(continue)

Molar absorbtivities from n - p * transitions are relatively low, and range from 10 to100

L mol -1 cm -1 . p - p * transitions normally give molar absorbtivities between 1000

and 10,000 L mol -1 cm -1

.

The corresponding absorption

band

R band (group type,德文Radikalartig) originated from n - p * transition. The maximum absorption wavelength > 270 nm, є max < 100

Example:

Acetone λ max 279 nm, є max =15

The corresponding absorption

band

K band (conjugation band, 德文Konjuierte)

form p - p * transition.

Example:

Dienes

Acetophenone

High є max ( > 10 4 )

The corresponding absorption

band

B band (Benzene band, Benzenoid bands) from the p - p * transition of Benzene. Broad band with fine structure between 230 270 nm. This band can be used to identify aromatic compound.

The corresponding absorption

band

E band (Ethylenic bands) also from p - p transition of ethylenic band in benzene

*

E1 band and E2 band

The corresponding absorption band • E band (Ethylenic bands) also from p - p transition of

Solvent effect

The solvent in which the absorbing

species is dissolved also has an effect on

the spectrum of the species.

Peaks resulting from n -p * transitions are shifted to shorter wavelengths (blue shift) with increasing solvent polarity. This arises from increased solvation of the lone pair, which lowers the energy of the n orbital.

Solvent effect (cont)

The reverse (i.e. red shift) is seen for p - p transitions. This is caused by attractive

*

polarisation forces between the solvent and the absorber, which lower the energy levels of both the excited and unexcited states. This effect is

greater for the excited state, and so the energy

difference between the excited and unexcited states is slightly reduced - resulting in a small red shift.

This effect also influences n -p * transitions but is overshadowed by the blue shift resulting from solvation of lone pairs.

Choice of Solvent

Solvent

Minimum

Solvent

Minimum

Solvent

Minimum

Wavele-

Wavelength

Wavelength

ngth (nm)

(nm)

(nm)

Acetonitrile

190

water

191

cyclohexane

195

hexane

195

methanol

201

ethanol

204

ether

215

methylene

220

Chloroform

237

chloride

carbon

257

       

tetrachloride

2.3

UV spectra and molecular

structure

The absorbing groups in a molecule are called chromophores

A molecule containing a chromophore is called a chromogen

An auxochrome does not itself absorb radiation, but can enhance the absorption

Bathochromic shift red shift Hypsochromic shift blue shift Hyperchromism an increase in absorption Hypochromism a decrease in absorption

2.3

UV spectra and molecular

structure

Chromophore

l max Transition

Alkanes

~ 150

s to s *

Alkenes

~ 175

p to p *

Alkynes

~ 170

Carbonyls

~ 188

alcohols, ethers

~ 185

h to s *

Amines

~ 195

sulfur compounds

~ 195

Carbonyls

~ 285

h to p *

Woodward-Fieser Rules for

Dienes

Homoannular

Parent Increments for:

(cisoid) l=253 nm

Heteroannular (transoid) l=214 nm

Double bond extending conjugation

30

30

Alkyl substituent or ring residue

5

5

Exocyclic double bond

5

5

Woodward-Fieser Rules for

Dienes

Homoannular

Parent Increments for:

(cisoid) l=253 nm

Heteroannular (transoid) l=214 nm

-OC(O)CH 3

0

0

-OR

6

6

Cl, -Br

5

5

-NR 2

60

60

-SR

30

30

Woodward's Rules for Conjugated

Carbonyl Compounds

d

g

b

a

- C = C C = C C = O |

R

Woodward's Rules for Conjugated

Carbonyl Compounds

Base values:

X = R

Six-membered ring or acyclic parent enone

Five-membered ring parent enone Acyclic dienone

l=215 nm l=202 nm l=245 nm

X = H

l=208 nm

X = OH, OR

l=193 nm

Increments for:

Double bond extending conjugation

30

Exocyclic double bond

5

Endocyclic double bond in a 5- or 7-membered ring for X = OH, OR

Homocyclic diene component

5

39

Woodward's Rules for Conjugated

Carbonyl Compounds

Alkyl substituent or ring residue

a

10

b

12

Polar groupings:

g or higher

18

-OH

a

35

b

30

d

50

-OC(O)CH 3

a,b,g,d 6

-OCH 3

a

35

b

30

g

17

d

31

Woodward's Rules for Conjugated

Carbonyl Compounds

-Cl

a15

b,g,d

12

-Br

b

30

a,g,d

25

-NR 2

b95

Solvent correction * :

* Solvent shifts for various solvents:

Solvent

l max shift (nm)

water

+ 8

chloroform

- 1

ether

- 7

cyclohexane

- 11

dioxane

- 5

hexane

- 11

Woodward's Rules for Aromatic

Compounds

1. Absorption for Mono-Substituted Benzene Derivatives

 

E

K

B

R

(e>30000)

(e~10000)

(e~300)

(e~50)

Electronic Donating Substituents

 

none

184

204

254

-R

189

208

262

-OH

211

270

-OR

217

269

-NH 2

230

280

Woodward's Rules for Aromatic

Compounds

 

E

K

B

R

Electronic Withdrawing Substituents

 

-F

204

254

-Cl

210

257

-Br

210

257

-I

207

258

-NH 3 +

203

254

Woodward's Rules for Aromatic

Compounds

E p-Conjugating Substituents

K

B

R

-C=CH 2

248

282

-CCH

202

248

278

-C 6 H 5

250

-CHO

242

280

328

-C(O)R

238

276

320

-CO 2 H

226

272

-CN

224

271

-NO 2

252

280

330

Woodward's Rules for Aromatic

Compounds

The adsorption band would have red shift and disappearance of B band fine structure with Mono-Substitution (F is an exception) and Di-Substituted Benzene

UV-vis Spectrophotometer

Single-Beam UV-Vis Spectrophotometer

Single-Beam spectrophotometers are often sufficient for making quantitative absorption measurements in the UV-Vis spectral region.

Single-beam spectrophotometers can

utilize a fixed wavelength light source or a

continuous source.

Single-Beam UV-Vis

Spectrophotometer

The simplest instruments use a single-

wavelength light source, such as a light-

emitting diode (LED), a sample container, and a photodiode detector.

Instruments with a continuous source have a dispersing element and aperture or slit to select a single wavelength before the light passes through the sample cell.

Dual-Beam uv-vis

Spectrophotometer

In single-beam Uv-vis absorption spectroscopy, obtaining a spectrum requires manually measuring the transmittance of the sample and solvent at each wavelength. The double-beam design greatly simplifies this process by measuring the transmittance of the sample and solvent simultaneously.

Instrumentation

The dual-beam design greatly simplifies this

process by simultaneously measuring P and Po

of the sample and reference cells, respectively. Most spectrometers use a mirrored rotating chopper wheel to alternately direct the light

beam through the sample and reference cells.

The detection electronics or software program can then manipulate the P and Po values as the wavelength scans to produce the spectrum of

absorbance or transmittance as a function of wavelength.

Array-Detector

Spectrophotometer

Array-detector spectrophotometers allow rapid recording of absorption spectra.

Dispersing the source light after it passes through a sample allows the use of an array detector to simultaneously record the transmitted light power at multiple wavelengths.

There are a large number of applications where absorbance spectra must be recorded very quickly. Some examples include HPLC detection, process monitoring, and measurement of reaction kinetics.

Instrumentation

These spectrometers use photodiode arrays (PDAs) or charge-coupled devices (CCDs) as

the detector. The spectral range of these array detectors is typically 200 to 1000 nm. The light

source is a continuum source such as a

tungsten lamp.

All wavelengths pass through the sample. The light is dispersed by a diffraction grating after the sample and the separated wavelengths fall on different pixels of the array detector.

Instrumentation

The resolution depends on the grating, spectrometer design, and pixel size, and is

usually fixed for a given instrument.

Besides allowing rapid spectral recording, these instruments are relatively small and robust. Portable spectrometers have been developed that use optical fibers to deliver light to and from a sample.

These instruments use only a single light beam, so a reference spectrum is recorded and stored in memory to produce transmittance or absorbance spectra after recording the sample

spectrum.

UV spectra analysis procedure

• It’s impossible to conclude the molecular

structure directly from it’s UV spectrum

UV spectra can be applied to identify the types, numbers and position of

chromophores and auxochrome; saturated and unsaturated compounds;

Identification of organic

compounds with UV

If no absorption peaks between 200 ~ 400 nm were detected, there isn’t any

conjugate double bond and C=O group.

Most probably it’s a saturated compound

If there is a weak peak (ε=10~100) between 270 ~ 350 nm, and no other peaks detected over 200 nm. It may contain >C=O, >C=C-O- or >C=C-N< etc. The weak peak is from n -p * transition

Identification of organic

compounds with UV

If there are a lot of peaks in UV region, some of

them are even within the visible region, the

compound may have long conjugation bonds

When l max is over 250 nm, ε is between 1000 ~ 10000, the compound may contain aromatic

structure

ε between 10000 ~ 20000 for the long wave absorption peak maybe conjugated diene or

carbonyl compounds