Spektroskopi UV dan

UV-Vis
Disusun oleh:
Sugeng Triono

Disampaikan pada:
Kuliah Elusidasi Struktur Kimia Organik
FMIPA UGM Yogyakarta

Spektroskopi
Ilmu yang mempelajari interaksi energi
dengan materi
Alat untuk mengimplementasikan
spektroskopi adalah spektrometer
Apa beda spektrometer dan
spektrofotometer?

Absorption and Emission

Absorption

Emission

Absorption: A transition from a lower level to a higher

level with transfer of energy from the radiation field to
an absorber, atom, molecule, or solid.
Emission: A transition from a higher level to a lower
level with transfer of energy from the emitter to the
radiation field. If no radiation is emitted, the transition
from higher to lower energy levels is called
nonradiative decay.
http://www.chemistry.vt.edu/chem-ed/spec/spectros.html

Where in the spectrum are these

transitions?

The Electromagnetic Spectrum

Warna
Cahaya yang dapat terlihat oleh manusia
disebut cahaya tampak
Merupakan campuran dari cahaya yang
mempunyai berbagai panjang gelombang
dari 380 nm hingga 780 nm

UV--Vis spectroscopy
UV
Electronic absorption spectroscopy

Energi
Secara umum:

E h . h.

Dimana:
E = energi (dalam Joule)
h = tetapan Planck = 6,624 x 10-34 J.s
= frekuensi (dalam hertz)
l = panjang gelombang (dalam meter)
C = kecepatan cahaya (3 x 108 m/s)
8

Dasar Spektroskopi Ultra Violet dan

Terlihat
Serapan cahaya oleh molekul dalam daerah spektrum Ultra Violet
dan Terlihat tergantung pada struktur elektronik dari molekul
Spektra Ultra Violet dan Terlihat berkaitan dengan transisi-transisi
di antara tingkatan-tingkatan energi elektronik
Serapan radiasi Ultra Violet dan Terlihat sering dikenal dengan
spektroskopi elektronik
Biasanya transisi tersebut antara orbital ikatan atau orbital
pasangan bebas dengan orbital non ikatan jenuh atau orbital anti
ikatan.
Dalam prakteknya, spektrometri ultraviolet digunakan terbatas
pada sistem-sistem terkonjugasi
9

THE NATURE OF ELECTRONIC

EXCITATIONS
When continuous radiation passes through a transparent material, a
portion of the radiation may be absorbed.
If that occurs, the residual radiation, when it is passed through a
prism, yields a spectrum with gaps in it, called an absorption
spectrum.
As a result of energy absorption, atoms or molecules pass from a
state of low energy (the initial, or ground state) to a state of higher
energy (the excited state).
The electromagnetic radiation that is absorbed has energy exactly
equal to the energy difference between the excited and ground states.

10

The excitation process

11

Electronic energy levels and

transitions
In the case of ultraviolet and visible spectroscopy, the transitions that
result in the absorption of electromagnetic radiation in this region of
the spectrum are transitions between electronic energy levels.
As a molecule absorbs energy, an electron is promoted from an
occupied orbital to an unoccupied orbital of greater potential energy.
Generally, the most probable transition is from the highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecular orbital
(LUMO).
The energy differences between electronic levels in most molecules
vary from 125 to 650 kJ/mole (kilojoules per mole).

12

Electronic energy levels and

transitions
For most molecules, the lowest-energy
occupied molecular orbitals are the s
orbitals, which correspond to s bonds.
The p orbitals lie at somewhat higher
energy levels, and orbitals that hold
unshared pairs, the nonbonding (n) orbitals,
lie at even higher energies.
The unoccupied, or antibonding orbitals (p *
and s *), are the orbitals of highest energy.
13

Tipe transisi elektron

Tiga tipe utama orbital molekul: orbital sigma (),
orbital phi (p) dan orbital terisi namun tidak
berikatan (n).
s*

Tidak terisi elektron

p*
Energi

Orbital atom

p
s
Orbital molekul

Orbital atom

Terisi elektron

Electronic energy levels and

transitions

15

In all compounds other than alkanes, the electrons may

undergo several possible transitions of different
energies. Some of the most important transitions are

16

Klasifikasi transisi serapan

elektronik
Kromofor, digunakan untuk menyatakan gugus
tak jenuh kovalen yang dapat menyerap radiasi
dalam daerah-daerah UV/vis
Auxokrom: Gugus jenuh yang bila terikat pada
kromofor mengubah panjang gelombang dari
intensitas serapan maksimum. Ciri auxokrom
adalah heteroatom yang langsung terikat pada
kromofor (-Cl; -OH; -NH2; dan OCH3)

17

Electron transitions

Analisis Kuantitatif
Secara kuantitatif, berkas radiasi dikenakan
pada cuplikan dan intensitas radiasi yang
ditransimsikan dapat diukur
Radiasi yang diserap ditentukan dengan
membandingkan intensitas dari berkas
radiasi yang ditransmisikan bila spesies
penyerap tidak ada (blanko) terhadap
intensitas yang ditransmisikan bila spesies
penyerap ada (sampel/cuplikan)
19

 Kekuatan radiasi (intensitas) dari berkas

cahaya sebanding dengan jumlah foton per
detik yang melalui satuan luas penampang
Jika foton yang mengenai cuplikan dan
tenaganya sama dengan yang dibutuhkan
untuk menyebabkan terjadinya perubahan
tenaga, maka serapan dapat terjadi
Kekuatan radiasi akan turun dengan adanya
hamburan dan pantulan, tetapi penurunan ini
sangat kecil bila dibandingkan dengan
serapan itu sendiri
Elusidasi Struktur
Organik

Sugeng Triono, FMIPA UGM

20

Prinsip kerja alat

Prinsip kerja alat

I0

detector

monochromator/
beam splitter optics

I0

reference

UV-VIS sources

sample

log(I0/I) = A

200

l, nm

I0

22

Hukum Kuantitatif
It

dI
I I - k 0 c db
0
Keterangan:
I0 = Intensitas cahaya sebelum melalui cuplikan
It = Intensitas cahaya setelah melalui cuplikan
c = konsentrasi
b = panjang cuplikan (panjang kuvet)

Catatan:
Tanda negatif menyatakan penurunan intensitas cahaya
23

It

dI
I I - k 0 c db
0

sehingga

It
ln - k c b
I0

It
2,303 log - k b c
I0
It
k
log b c -e b c
I0
2,303
Dimana e adalah serapan molar (koefisien ekstingsi
molar). Jika konsentrasi diberikan dalam g/L, e maka
diganti dengan a (serapan spesifik)
24

Pengertian It/I0 disebut sebagai transmitansi (T) yang

merupakan kekuatan cahaya masuk yang di
transmisikan oleh cuplikan
Persen Transmitansi didefinisikan sebagai 100 x T
- log T didefinisikan sebagai Absorbansi (A) atau
kerapatan optik

It
log - e b c
I0

sehingga

log T - e b c
- log T e b c

A - log T e b c

Hukum Beer-Lambert, hukum

Bougner-Beer
(dikenal sebagai Hukum Beer)

25

Dalam Hukum Beer

Dalam penurunan hukum ini dianggap bahwa:
1) Radiasi yang masuk adalah monokromatis
2) Spesies penyerap berkelakuan tak tergantung
satu terhadap lainnya dalam proses penyerapan
3) Penyerapan terjadi dalam volume yang
mempunyai luas penampang yang sama
4) Dengan radiasi tenaga adalah cepat (tidak terjadi
flouresensi)
5) Indeks bias tidak tergantung pada konsentrasi
(tidak berlaku pada konsentrasi yang tinggi)
26

Pergeseran serapan panjang

gelombang
Pergeseran batokromik: Pergeseran serapan ke arah
panjang yang lebih panjang disebabkan substitusi
atau pengaruh pelarut (pergeseran merah)
Pergeseran hipsokromik: Pergeseran serapan ke
arah panjang yang lebih pendek disebabkan
substitusi atau pengaruh pelarut (pergeseran biru)
Efek hiperkromik: Kenaikan dalam intensitas
serapan
Efek hipokromik: Penurunan dalam intensitas
serapan
27

Hyperchromic

Pergeseran serapan panjang gelombang

E
Hypsochromic
Hypochromic

200 nm

Bathochromic

700 nm
28

Menghitung serapan maksimum

Woodward-Fieser telah berhasil menentukan
rumus-rumus empiris untuk menghitung l max
Tiga jenis sistem yang dapat ditentukan:
1) Diena bukan siklis atau diena yang terdapat dalam
sistem cincin yang tidak bergabung
2) Diena atau poliena dalam sistem cincin yang bergabung
3) Enon dan dienon yang terkonjugasi

29

THE WOODWARDFIESER
RULES FOR DIENES

30

UV Spectroscopy
IV. Structure Determination
A. Dienes
1. General Features
The Y2 Y3* transition is observed as an intense absorption (e =
20,000+) based at 217 nm within the observed region of the UV
While this band is insensitive to solvent (as would be expected) it is
subject to the bathochromic and hyperchromic effects of alkyl
substituents as well as further conjugation
Consider:

lmax = 217

253

220

227

227

256

263

nm

31

UV Spectroscopy
IV. Structure Determination
A. Dienes
2. Woodward-Fieser Rules - Dienes
For example:
Isoprene - acyclic butadiene =
one alkyl subs.
Experimental value

Allylidenecyclohexane
- acyclic butadiene =
one exocyclic C=C
2 alkyl subs.
Experimental value

217 nm
+ 5 nm
222 nm
220 nm

217 nm
+ 5 nm
+10 nm
232 nm
237 nm
32

Woodward-Fieser Rules for Dienes

Parent

Homoannular
l=253 nm

Heteroannular
l =214 nm
l =217 (acyclic)

Increments for:
Double bond extending conjugation
Alkyl substituent or ring residue
Exocyclic double bond
Polar groupings:
-OC(O)CH3
-OR
-Cl, -Br
-NR2
-SR

Homoannular

heteroannular

+30
+5
+5

C
C C
C

+0
+6
+5
+60
+30

acyclic

exocyclic

UV Spectroscopy
IV. Structure Determination
A. Dienes
3. Woodward-Fieser Rules Cyclic Dienes
There are two major types of cyclic dienes, with two different base values
Heteroannular (transoid):

e = 5,000 15,000
base lmax = 214

Homoannular (cisoid):

e = 12,000-28,000
base lmax = 253

The increment table is the same as for acyclic butadienes with a couple
additions:
Group

Additional homoannular
Where both types of diene
are present, the one with
the longer l becomes the
base

Increment
+39

34

UV Spectroscopy
IV. Structure Determination
A. Dienes
3. Woodward-Fieser Rules Cyclic Dienes
For example:
1,2,3,7,8,8a-hexahydro-8a-methylnaphthalene
heteroannular diene =
214 nm

3 alkyl subs. (3 x 5)

+15 nm

1 exo C=C

+ 5 nm
234 nm

Experimental value

235 nm

35

UV Spectroscopy
IV. Structure Determination
A. Dienes
3. Woodward-Fieser Rules Cyclic Dienes
heteroannular diene =
4 alkyl subs. (4 x 5)
1 exo C=C

239 nm

C OH
O

homoannular diene =
4 alkyl subs. (4 x 5)
1 exo C=C
C OH
O

214 nm
+20 nm
+ 5 nm

253 nm
+20 nm
+ 5 nm
278 nm

36

Tentukan maksimum untuk molekul berikut

(b)

(a)
CH3
CH

(c)

H3C

CH3

CH3

(d)

COOH
37

UV Spectroscopy
Structure Determination
Enones
1. General Features
For auxochromic
substitution on the
carbonyl,
pronounced
hypsochromic shifts
are observed for the
n p* transition
(lmax):

38

UV Spectroscopy
Structure Determination
Enones

C C C
O

C C C C C
O
Increment

Group
6-membered ring or acyclic enone

Base 215 nm

5-membered ring parent enone

Base 202 nm

Acyclic dienone

Base 245 nm

30

Double bond extending conjugation

Alkyl group or ring residue

, , and higher

10, 12, 18

-OH

, , and higher

35, 30, 18

-OR

, , ,

35, 30, 17, 31

, ,

-Cl

15, 12

-Br

25, 30

95

-O(C=O)R

-NR2
Exocyclic double bond
Homocyclic diene component

5
39

39

UV Spectroscopy
IV. Structure Determination
B. Enones
2. Woodward-Fieser Rules - Enones
Aldehydes, esters and carboxylic acids have different base
values than ketones
Unsaturated system

Base Value

Aldehyde

208

With or alkyl groups

220

With , or , alkyl groups

230

With ,, alkyl groups

242

Acid or ester
With or alkyl groups

208

With , or , alkyl groups

217

Group value exocyclic , double bond

+5

Group value endocyclic , bond in 5 or 7

membered ring

+5

40

UV Spectroscopy
IV. Structure Determination
B. Enones
2. Woodward-Fieser Rules - Enones
Unlike conjugated alkenes, solvent does have an effect on lmax
These effects are also described by the Woodward-Fieser rules
Solvent correction
Water

Increment
+8

Ethanol, methanol

Chloroform

-1

Dioxane

-5

Ether

-7

Hydrocarbon

-11

41

UV Spectroscopy
IV. Structure Determination
B. Enones
2. Woodward-Fieser Rules - Enones
Some examples keep in mind these are more complex than dienes
cyclic enone =
215 nm
O
2 x - alkyl subs. (2 x 12) +24 nm
239 nm

Experimental value

238 nm

cyclic enone =
extended conj.
-ring residue
-ring residue
exocyclic double bond

215 nm
+30 nm
+12 nm
+18 nm
+ 5 nm
280 nm

Experimental

280 nm

42

UV Spectroscopy
IV. Structure Determination
B. Enones
2. Woodward-Fieser Rules - Enones
Take home problem can these two isomers be discerned by
UV-spec

O
O

Eremophilone

allo-Eremophilone

43

UV Spectroscopy
IV. Structure Determination
C. Aromatic Compounds
1. General Features
Substitution, auxochromic, conjugation and solvent effects can
cause shifts in wavelength and intensity of aromatic systems
similar to dienes and enones
However, these shifts are difficult to predict the formulation of
empirical rules is for the most part is not efficient (there are
more exceptions than rules)
There are some general qualitative observations that can be
made by classifying substituent groups --

44

UV Spectroscopy
IV. Structure Determination
C. Aromatic Compounds
2. Substituent Effects
a. Substituents with Unshared Electrons

pH can change the nature of the substituent group

deprotonation of oxygen gives more available n-pairs,

lowering transition energy

protonation of nitrogen eliminates the n-pair,

raising transition energy
Primary

Secondary

Substituent

l max

l max

-H

203.5

7,400

254

204

-OH

211

6,200

270

1,450

-O-

235

9,400

287

2,600

-NH2

230

8,600

280

1,430

-NH3+

203

7,500

254

169

-C(O)OH

230

11,600

273

970

-C(O)O-

224

8,700

268

560
45

UV Spectroscopy
IV. Structure Determination
C. Aromatic Compounds
2. Substituent Effects
b. Substituents Capable of p-conjugation

When the substituent is a p-chromophore, it can interact with

the benzene p-system

With benzoic acids, this causes an appreciable shift in the

primary and secondary bands

For the benzoate ion, the effect of extra n-electrons from the
anion reduces the effect slightly
Primary

Secondary

Substituent

l max

l max

-C(O)OH

230

11,600

273

970

-C(O)O-

224

8,700

268

560

46

UV Spectroscopy
IV. Structure Determination
C. Aromatic Compounds
2. Substituent Effects
c. Electron-donating and electron-withdrawing effects

Electron withdrawing

Electron donating

Primary

Secondary

Substituent

l max

l max

-H

203.5

7,400

254

204

-CH3

207

7,000

261

225

-Cl

210

7,400

264

190

-Br

210

7,900

261

192

-OH

211

6,200

270

1,450

-OCH3

217

6,400

269

1,480

-NH2

230

8,600

280

1,430

-CN

224

13,000

271

1,000

C(O)OH

230

11,600

273

970

-C(O)H

250

11,400

-C(O)CH3

224

9,800

-NO2

269

7,800
47

UV Spectroscopy
IV. Structure Determination
C. Aromatic Compounds
2. Substituent Effects
d. Di-substituted and multiple group effects

If the two electonically dissimilar groups are ortho- or

meta- to one another, the effect is usually the sum of
the two individual effects (meta- no resonance; orthoO
R
steric hind.)

For the case of substituted benzoyl derivatives, an

empirical correlation of structure with observed lmax
has been developed

This is slightly less accurate than the WoodwardFieser rules, but can usually predict within an error of
5 nm

48

UV Spectroscopy
IV. Structure Determination
C. Aromatic Compounds
2. Substituent Effects
d. Di-substituted and multiple group effects

Parent Chromophore

lmax

R = alkyl or ring residue

246

R=H

250

R = OH or O-Alkyl

230

Substituent increment
G

Alkyl or ring residue

10

-O-Alkyl, -OH, -O-Ring

25

-O-

11

20

78

-Cl

10

-Br

15

-NH2

13

13

58

-NHC(O)CH3

20

20

45

-NHCH3
-N(CH3)2

73
20

20

85

49