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UV - VISIBLE SPECTROSCOPY
Syllabus:
• Electronic transition
• Chromophores and Auxochromes
• Factors influencing position and intensity of absorption bands
• Effect of solvent on spectra
• Absorption spectra of Dienes, Polyene , Unsaturated carbonyl
compounds
• Woodward Fieser rules
Dr. K. SIVAKUMAR
Department of Chemistry
SCSVMV University
chemshiva@gmail.com
1
n
Electromagnetic Waves - Terminologies
Wavelength (λ): Wavelength is the distance between the consecutive peaks or crests
Frequency (n): Frequency is the number of waves passing through any point per second.
3
n
Electromagnetic Waves - Terminologies
1 n
=n =
Where,
l c
l is wave length
n is wave number
n is frequency
4
Electromagnetic Spectral regions
nm 10-4 to 10-2 10-2 to 100 100 to 102 102 to 103 103 to 105 105 to 107 107 to 109
EM
waves g-rays X-rays UV Visible IR Microwave Radio
5
Electromagnetic Spectrum
E = hn h – Planck’s constant
6
www.spectroscopyNOW.com
The Electromagnetic wave lengths & Some examples
7
Electromagnetic radiation sources
UV spec.
Ultraviolet Hydrogen discharge lamp
Visible spec.
Visible tungsten filament lamp
IR spec.
Infrared rare-earth oxides rod
ESR spec.
Microwave klystron valve
NMR spec.
Radio wave magnet of stable field strength
8
Electromagnetic Spectrum – Type of radiation and Energy change involved
9
Electromagnetic Spectrum – Type of radiation and Energy change involved
10
Electromagnetic Spectrum – Type of radiation and Energy change involved
11
Effect of electromagnetic radiations on chemical substances
The absorption spectrum of an atom often contains sharp and clear lines.
12
Effect of electromagnetic radiations on chemical substances
This is due to the fact that molecules have large number of energy levels and
certain amount of energy is required for transition between these energy levels.
13
Effect of electromagnetic radiations on chemical substances
14
Effect of electromagnetic radiations on chemical substances
Rotational transition
Microwave and far IR radiations bring about changes in the rotational energies
of the molecule
15
Effect of electromagnetic radiations on chemical substances
Vibrational transition
Examples:
Example:
Vibrating HCl molecule
16
Effect of electromagnetic radiations on chemical substances
Electronic transition
UV and Visible radiations bring about changes in the electronic transition of a molecule
17
Effect of electromagnetic radiations on chemical substances
18
Effect of electromagnetic radiations on chemical substances
19
The Ultraviolet region [10 – 800nm]
20
The Ultraviolet region
• Electromagnetic spectral region from 100 – 200nm can be studied in evacuated system
and this regions is termed as “vacuum UV”
• The atmosphere absorbs the hazardous high energy UV <200nm from sunlight
• Excitation (and maximum separation) of - electrons occurs in 120 – 200nm
21
The Visible region
22
VISIBLE region in Electromagnetic Spectrum
23
UV - VISIBLE SPECTROSCOPY
• In UV - Visible Spectroscopy, the sample is irradiated with the broad
spectrum of the UV - Visible radiation
24
Lambert’s law
fraction of the monochromatic light absorbed by a
homogeneous medium is independent of the intensity of the
incident light and each successive unit layer absorbs an equal
fraction of the light incident on it
Lambert
Beer’s law
Beer
25
Beer–Lambert law / Beer–Lambert– Bouguer law / Lambert – Beer law
log (I0/I) = c l = A
Where,
I0 - the intensity of incident light
I - the intensity of transmitted light
- molar absorptivity / molar extinction coefficient in cm 2 mol-1 or L mol-1 cm-1.
c - concentration in mol L-1
l - path length in cm
A - absorbance (unitless)
Molar absorptivity
26
Absorption intensity
max = 20000
27
Generalizations Regarding l max
Exceptions: some nitro-, azo-, diazo-, and nitroso-compounds will absorb visible light.
28
Generalizations Regarding max
Substitution on the aromatic nucleus by a functional group which extends the length of
the chromophore may give bands with max > 10,000 along with some which still have
max < 10,000.
29
Beer–Lambert law / Beer–Lambert– Bouguer law / Lambert – Beer law
Bouguer
Actually investigated the
range of absorption Vs
thickness of medium
?
Lambert
31
Bonding and anti-bonding formation from s atomic orbitals (Eg: H2 molecule)
Bonding between two hydrogen atoms One molecular orbital
with 2 electrons
2 atomic orbitals of
2 hydrogen atoms
32
Bonding and anti-bonding formation from s atomic orbitals (Eg: H2 molecule)
Lower energy
than original atomic orbitals
2 atomic orbitals of
2 hydrogen atoms
Bonding orbitals are lower in energy than its original (atoms) atomic orbitals.
Because, energy is released when the bonding orbital is formed,
i.e., hydrogen molecule is more energetically stable than the original atoms.
However, an anti-bonding orbital is less energetically stable than the original atoms.
A bonding orbital is stable because of the attractions between the nuclei and the electrons.
In an anti-bonding orbital there are no equivalent attractions - instead of attraction you get repulsions.
There is very little chance of finding the electrons between the two nuclei - and in fact half-way between the nuclei
there is zero chance of finding electrons. There is nothing to stop the two nuclei from repelling each other apart.
So in the hydrogen case, both of the electrons go into the bonding orbital, because that produces the greatest stability
33
- more stable than having separate atoms, and a lot more stable than having the electrons in the anti-bonding orbital.
Bonding and anti-bonding formation from p atomic orbitals
34
Bonding and anti-bonding formation from p atomic orbitals
35
Electronic Energy Levels
* (antibonding)
* (antibonding)
n (nonbonding)
Energy
(bonding)
(bonding)
36
Electronic Energy Levels
Graphically,
*
Unoccupied levels
*
Occupied levels
Molecular orbitals
37
Electronic Transitions
• The valence electrons in organic molecules are involved in bonding as
- bonds, - bonds or present in the non-bonding form (lone pair)
* Unoccupied levels
*
39
Types of Electronic Transitions
* (bonding to anti-bonding )
* (antibonding)
• * transition requires large energies * (antibonding)
in
far UV region in 120-200nm range.
n (nonbonding)
• Molar absorptivity: Low
max = 1000 - 10000
(bonding)
(bonding)
• Examples: Alkanes - transition @ 150nm
40
Types of Electronic Transitions
* (bonding to anti-bonding )
+ C_ +C _
*
C-C
_ C _
+ C C-C
41
Types of Electronic Transitions
Examples:
• Unsaturated compounds (bonding)
• double or triple bonds
• aromatic rings
• Carbonyl groups (bonding)
• azo groups
• Conjugated electrons max is high because the and * orbitals
are in same plane and consequently the
probability of jump of an electron from
Carbonyl * orbital is very high.
Azo
42
Types of Electronic Transitions
* (bonding to anti-bonding )
_
+
C C
_
*
+
+
C C
_
43
Types of Electronic Transitions
(bonding)
44
Types of Electronic Transitions
• Examples:
• Compounds with double bonds involving unshared pair(s) of electrons
• Aldehydes, Ketones
• C=O, C=S, N=O etc.,
45
Types of Electronic Transitions
n * (non-bonding n to anti-bonding )
_
+
C O *
+ _
+
n(py)
C O
_
+
C C
_
46
Types of Electronic Transitions
n to
* (antibonding)
• Excitation of an electron in an unshared
pair on Nitrogen, oxygen, sulphur or
halogens to an antibonding orbital is
called n * transitions. n (nonbonding)
48
Types of Electronic Transitions
n * (non-bonding n to anti-bonding )
+ C_ +N _
*
C-N
_
C N n
+
_ C + N _ C-N
49
Types of Electronic Transitions
* (bonding to anti-bonding )
* (bonding to anti-bonding )
* (antibonding)
* (bonding to anti-bonding ) * (antibonding)
n * (non-bonding n to anti-bonding )
n (nonbonding)
n * (non-bonding n to anti-bonding )
(bonding)
(bonding)
Energy required for various transitions obey the order: * > n * > *> n *
50
Types of Electronic Transitions
• From the molecular orbital diagram it is clear that, In all compounds other than
alkanes there are several possible electronic transitions that can occur with different
energies.
*
* alkanes 150 nm
*
* carbonyls 170 nm
n * carbonyls 300 nm
51
Selection Rules
• Not all transitions that are possible in UV region are not generally observed.
• For an electron to transition, certain quantum mechanical constraints apply – these
are called “selection rules”.
• Here,
• For excited singlet state: S=0; therefore, 2S+1=1 - transition allowed
• For excited triplet state: S=1; therefore, 2S+1=3 - transition forbidden
52
Selection Rules
In other words, these excited states will have their energy minima
somewhere in between that of H2C=O and H3C-OH.
• To further complicate matters, “forbidden” transitions are sometimes observed (albeit at low intensity) due
to other factors. 53
Franck and Condon Principle
• Electronic transitions will take place only when the inter-nuclear distances are not
significantly different in the two states and where the nuclei have little or no velocity.
• Thus, the forbidden transitions may arise when the inter-nuclear distances are
significantly different in the two states and where the nuclei have significant velocity.
54
Origin and General appearance of UV bands
• When gaseous sample is irradiated with UV - Visible light and the spectrum is
recorded, a spectrum with number of closely spaced fine structure line is obtained.
• Usually electronic absorption spectrums are broader bands than IR or NMR bands.
55
Designation of UV bands
• The absorption bands in the UV - Visible spectrum may be designated either by using
electronic transitions [ *, *, *, n *, n *] or the
letter designation as given below.
• Shows low molar absorptivity ( max<100) and hypsochromic shift with an increase in
solvent polarity.
56
Designation of UV bands
B and E - bands
Examples:
• All benzenoid compounds exhibit E and B
bands representing * transitions.
The coloured substances owe their colour to the presence of one or more unsaturated
groups responsible for electronic absorption. These groups are called chromophores.
But, some of them (e.g, carbonyl) have less intense bands at higher wavelength due to
the participation of n electrons.
Methyl orange
58
Chromophores: examples
59
Auxochromes
An auxochromes is an auxillary group which interact with chromophore and deepens
colour; its presence causes a shift in the UV or visible absorption maximum to a longer
wavelength
60
Auxochromes: examples
61
Bathochromic shift (Red shift) - l max to longer wavelength
Example:
Ethylene : l max = 175nm
1-butene / isobutene : l max = 188 nm
62
Hypsochromic shift (Blue shift) - l max to Shorter wavelength
Example: Acetone
lmax = 279nm in hexane
lmax = 264.5nm in water
This blue shift results from hydrogen bonding which lowers the energy of the n orbital.
63
Hyperchromic effect - increased ( max) absorption intensity
64
Hypochromic effect - decreased ( max) absorption intensity
Example: intensities of primary and secondary bands of benzoic acid are decreased in
benzoate
65
Effect of substituents on l max and max
Shift to decreased
max
66
Isosbestic point
A point common to all curves produced in the spectra of a compound taken at various
pH values is called isosbestic point.
If one absorbing species, X, is converted to another absorbing species, Y, in a
chemical reaction, then the characteristic behaviour shown in the figure below is
observed.
Example: Absorption spectrum of 3.7×10-4 M methyl red as a function of pH between pH 4.5 and 7.1
log(I0/I) = A
UV-VIS sources I0 I1
sample
200 700
detector
l, nm
I
monochromator/
reference
beam splitter optics I0 I2
69
Instrumentation…
The beam splitter sends a separate band to a cell containing the sample
solution and a reference solution
70
Sample Handling
71
Solvents
acetonitrile 190
chloroform 240
cyclohexane 195
1,4-dioxane 215
95% ethanol 205
n-hexane 201
methanol 205
isooctane 195
water 190
72
Factors affecting the position of UV bands – 1. Non-conjugated alkenes
*
73
Factors affecting the position of UV bands – 1. Non-conjugated alkenes…
• From l max di-, tri & tetra substituted double bonds in acyclic and alicyclic
systems can be identified
74
Factors affecting the position of UV bands – 1. Non-conjugated alkenes…
H
Methyl groups also cause a
C bathochromic shift, even though they
H
C C H
are devoid of p-or n-Electrons
Example:
Ethylene and Butadiene
76
Factors affecting the position of UV bands
[i.e., From MOT, two atomic p orbitals, from two sp2 hybrid carbons combine to form two
MOs and * in ethylene,]
2*
p p
1
77
Factors affecting the position of UV bands - 2. Conjugated Dienes
Therefore, the following and * for ethylene and butadiene will be obtained.
4
*
2*
3
*
2
1
1
Ethylene Butadiene 78
Factors affecting the position of UV bands - 2. Conjugated Dienes
Butadiene, however, with four electrons has four available orbitals, two bonding (1 and 2) and two
antibonding (*3 and *4) orbitals.
The 1 bonding orbital encompasses all the four electrons over the four carbon atoms of the butadiene
system and is somewhat more stable than a single bonding orbital in ethylene.
The 2 orbital is also bonding orbital, but is of higher energy than the 1 orbital.
The two * orbitals (*3 and *4) are respectively, more stable ((*3) and less stable (*4) than the *
orbital of ethylene.
Energy absorption, with the appearance of an absorption band, can thus occur by a 2 (bonding) (*3
(antibonding transition. HOMO to LUMO), the energy difference of which (136 kcal/mole) is less than that
of the simple * transition of ethylene (176 kcal/mole) giving a lmax= 217 nm; (i.e., at a longer
wavelength).
It is to be expected that the greater the number of bonding orbitals, the lower will be the energy
between the highest bonding orbital and the lowest excited * orbital.
The obvious extension of this in terms of lmax is that the greater the number of conjugated double bonds,
the longer the wavelength of absorption.
79
Factors affecting the position of UV bands - 2. Conjugated Dienes
4
*
2*
3
*
136 kcal/mole
= 176 kcal/mole
2
1
1
ethylene
butadiene
hexatriene
octatetraene 81
Factors affecting the position of UV bands - 2. Conjugated Dienes - Types
• Homo-annular conjugated dienes: Both conjugated double bonds are in same ring
• Hetero-annular dienes: Conjugated double bonds are not present in same ring
82
Factors affecting the position of UV bands - 2. Conjugated Dienes - Types
Endocyclic
double bond
Exocyclic
double bond
83
Factors affecting the position of UV bands - 2. Conjugated Dienes - Types
A B
two double bonds are confined to two different rings.
Base l max=214 nm
• Base lmax= 214 nm (max = 5000-20000).
max = 5000-20000
84
Factors affecting the position of UV bands - 2. Conjugated Dienes - Types
2. Homoannular diene
In homoannular diene, the two conjugated double bonds are Base l max=253 nm
confined to a single ring. max = 5000-8000
i.e., the cyclic dienes are forced into an s-cis (cisoid) conformation.
Base lmax= 253 nm (max = 5000-8000).
Example:
Cyclopentadiene; lmax=228nm
Cycloheptadiene; lmax= 241nm
85
Factors affecting the position of UV bands - 2. Conjugated Dienes
H2C=CH-CH2-CH2-CH=CH2 CH3-CH=CH-CH=CH-CH3
1,5-Hexadiene 2,4-Hexadiene
(non-conjugated diene) (conjugated diene)
lmax = 178 nm lmax = 227 nm
86
Factors affecting the position of UV bands - 2. Conjugated Dienes
87
Factors affecting the position of UV bands - 2. Conjugated Dienes - Types
Example:
88
Factors affecting the position of UV bands - 2. Conjugation… with hetero atoms
89
Y1
Factors affecting the position of UV bands – 3. Effect of Geometrical isomerism - Steric effect
• In compounds where geometrical isomerism is possible.
Example:
trans - stilbene absorbs at longer wavelength [l max=295 nm] (low energy)
cis - stilbene absorbs at shorter wavelength [l max=280 nm] (high energy) due to the steric
effects.
• Coplanarity is needed for the most effective overlap of the - orbitals and increased ease of
the
* transition. The cis-stilbene is forced into a nonplanar conformation due to steric
effects.
90
Factors affecting the position of UV bands –
4. Effect of steric hindrance on coplanarity (steric inhibition of resonance)
• UV spectroscopy is very sensitive to distortion of the chromophore and consequently the steric
repulsions which oppose the coplanarity of conjugated -electron systems can easily be
detected by comparing its UV spectrum with that of a model compound.
• Distortion of the chromophore may lead to RED or BLUE shifts depending upon the nature of
the distortion.
91
Factors affecting the position of UV bands –
4. Effect of steric hindrance on coplanarity (steric inhibition of resonance)….
92
Factors affecting the position of UV bands –
4. Effect of steric hindrance on coplanarity (steric inhibition of resonance)…..
H H
93
Factors affecting the position of UV bands – 5. Effect of Solvents
• Such solvent shifts are due to the differences in the relative capabilities of the
solvents to solvate the ground and excited states of a molecule.
94
Factors affecting the position of UV bands – 5. Effect of Solvents…
The following pattern of shifts are generally observed for changes to solvents of
increased polarity:
95
Factors affecting the position of UV bands – 5. Effect of Solvents…
In n * transition the ground state is more polar than excited state. The
hydrogen bonding with solvent molecules takes place to a lesser extent
with the carbonyl group in the excited state.
B
* D
AB < CD
n
A
Non-polar solvent C
Polar solvent
Shorter wavelength
96
Factors affecting the position of UV bands – 5. Effect of Solvents…
Example:
B
* D
AB > CD
A
Non-polar solvent C
Polar solvent
97
Longer wavelength
Factors affecting the position of UV bands – 5. Effect of Solvents…
b) If the group (carbonyl) is more polar in the excited state, the absorption is
shifted to longer wavelength with increase in polarity of the solvent which
helps in stabilizing the non-bonding electrons in the excited state.
98
Factors affecting the position of UV bands – 6. Conformation and geometry in polyene systems
• The position of absorption depends upon the length of the conjugated system.
• Longer the conjugated system, higher will be the absorption maximum and larger
will be the value of the extinction coefficient.
• This is illustrated by the naturally occurring bixin (`all trans’ methyl carotenoid)
and its isomer with a central cis-double bonds.
• In the latter the long wavelength band is weakened and a diagnostically useful
`cis-band` probably due to partial chromophore, appears at shorter wavelength.
99
Absorption spectra of Unsaturated carbonyl compounds……. Enones
n * transitions in addition to *
Low intensity is due to the fact this transition is forbidden by the selection rules
100
Absorption spectra of Unsaturated carbonyl compounds……. Enones
101
Absorption spectra of Unsaturated carbonyl compounds……. Enones
*
It has been determined
from spectral studies,
n C O
that carbonyl oxygen
more approximates sp
rather than sp2 !
O
102
Absorption spectra of Unsaturated carbonyl compounds……. Enones
O
293 nm
H
This is explained by the inductive
O withdrawal of electrons by O, N or
CH3 279 nm halogen from the carbonyl carbon – this
causes the n-electrons on the carbonyl
Blue shift
O oxygen to be held more firmly
Cl
235 nm
It is important to note this is different from
O
l max the auxochromic effect on * which
214 nm extends conjugation and causes a
NH2
bathochromic shift
O
204 nm In most cases, this bathochromic shift is not
O enough to bring the * transition into
the observed range
O
204 nm
103
OH
Absorption spectra of Unsaturated carbonyl compounds……. Enones
Conversely, if the C=O system is conjugated both the n * and * bands are
Bathochromically (Red) shifted
104
Absorption spectra of Unsaturated carbonyl compounds……. Enones
Conjugation effects are apparent; from the MO diagram for a conjugated enone:
Y 4*
* *
Y 3*
n n
Y2
Y1
O O
105
Absorption spectra of Alkanes - Miscellaneous
Alkanes – only posses -bonds and no lone pairs of electrons, so only the high
energy * transition is observed in the far UV
C C
*
C C
106
Absorption spectra of Aliphatic compounds - Miscellaneous
Alcohols, ethers, amines and sulfur compounds – in the cases of simple, aliphatic
examples of these compounds the n * is the most often observed transition;
like the alkane * it is most often at shorter l than 200 nm
Note how this transition occurs from the HOMO to the LUMO
C N
* CN
C N
nN sp
3
C N anitbonding
orbital
CN C N
107
Woodward – Fieser rules
Robert B. Woodward
Nobel Prize in Chemistry : 1965
108
Woodward – Fieser rules
Woodward-Fieser Rules
This work was distilled by Scott in 1964 into an extensive treatise on the
Woodward-Fieser rules in combination with comprehensive tables and
examples – (A.I. Scott, Interpretation of the Ultraviolet Spectra of Natural
Products, Pergamon, NY, 1964)
109
Woodward – Fieser rules for Dienes
The rules begin with a base value for lmax of the chromophore being observed:
Group Increment
Extended conjugation +30
Each exo-cyclic C=C +5
Alkyl +5
-OCOCH3 +0
-OR +6
-SR +30
-Cl, -Br +5
-NR2 +60
110
Woodward – Fieser rules for Dienes – Examples -1 & 2
111
Woodward – Fieser rules for Dienes – Problem - 1
113
Woodward – Fieser rules for Cyclic Dienes
The increment table is the same as for acyclic butadienes with a couple additions:
Group Increment Group Increment
Additional homoannular +39 Extended conjugation +30
Where both types of Each exo-cyclic C=C +5
diene are present, the
one with the longer l Alkyl +5
becomes the base -OCOCH3 +0
-OR +6
-SR +30
-Cl, -Br +5
-NR2 +60 114
Woodward – Fieser rules for Cyclic Dienes – Example-4
1,2,3,7,8,8a-hexahydro-8a-methylnaphthalene
1 exo C=C = + 5 nm
Calculated value 234 nm
Observed value 235 nm
115
Woodward – Fieser rules for Dienes – Problem - 2
Group Increment
Solution:
Extended conjugation +30
Heteroannular diene = 214 nm
Each exo-cyclic C=C +5
Ring residues /
Alkyl +5
Alkyl substitution 3x5 = + 15 nm
-OCOCH3 +0
Exocyclic C=C bond 1 x 5 = + 5 nm
-OR +6
-SR +30 Calculated value = 234 nm
-Cl, -Br +5 Observed value = 247 nm
-NR2 +60
116
Woodward – Fieser rules for Cyclic Dienes – Example-5
117
Woodward – Fieser rules for Cyclic Dienes – Example-6
118
Woodward – Fieser rules for Cyclic Dienes – Example-7
119
Woodward – Fieser rules for Dienes – Problem - 3
Group Increment
Solution:
Additional homoannular +39
Extended conjugation +30
Homoannular diene = 253 nm
Extended conjugation 1 x 30 = +30 nm
Each exo-cyclic C=C +5
Alkyl substitution 2x5 = + 10 nm
Alkyl +5
Calculated value = 293 nm
-OCOCH3 +0
-OR +6
-SR +30
-Cl, -Br +5
-NR2 +60 120
Woodward – Fieser rules for Cyclic Dienes – Example-8
121
Woodward – Fieser rules for Dienes – Examples – 9,10 & 11
122
Woodward – Fieser rules for Cyclic Dienes – PRECAUTIONS
123
Woodward – Fieser rules for Enones
g
C C C C C C C C
O O
Group Increment
6-membered ring or acyclic enone Base 215 nm
5-membered ring parent enone Base 202 nm
Acyclic dienone Base 245 nm
Aldehydes, esters and carboxylic acids have different base values than ketones
Aldehyde 208
Acid or ester
125
Woodward – Fieser rules for Enones
Water +8
Ethanol, methanol 0
Chloroform -1
Dioxane -5
Ether -7
Hydrocarbon -11
126
Woodward – Fieser rules for Enones – Examples – 12 & 13
Some examples – keep in mind these are more complex than dienes
O enone =
cyclic 215 nm
2 x - alkyl subs. (2 x 12) +24 nm
Calculated value 239 nm
Experimental value 238 nm
cyclic
R enone = 215 nm
extended conj. +30 nm
-ring residue +12 nm -ring
residue +18 nm exocyclic double bond + 5 nm
280 nm
O
Experimental 280 nm
127
Woodward – Fieser rules for Enones – Problem – 4
g
C C C C C C C C
O O
g
C C C C C C C C
O O
Group Increment
6-membered ring or acyclic enone Base 215 nm
5-membered ring parent enone Base 202 nm
Acyclic dienone Base 245 nm
130
UV Spectroscopy – For Assignment
2. Woodward Fieser rules for Polyenes – Rules and calculation for atleast 2 polyenes
131
UV Spectroscopy - References
Dr. K. SIVAKUMAR
Department of Chemistry
134
SCSVMV University
chemshiva@gmail.com