LESSON SIX ULTRA VIOLET SPECTROSCOPY

6.1 Introduction
Ultra violet spectroscopy is concerned with transitions between electronic energy levels and
absorption of ultraviolet radiation by the molecule. Since each electronic level is associated
with numbers of vibrational and rotational energy levels, transitions from one electronic level
to another electronic level is always accompanied by rotational and vibrational transitions.
As a result, the resulting spectra will be complex showing broad absorption bands.

6.2 Lesson Learning Outcomes

By the end of this lesson, you will be able to:

(a) Explain theory of UV spectroscopy
(b) Describe various elctronic transitions in molecules
(c) Describe chromophores, auxochromes, conjugation, bathochromic and hypsochromic
shift, and hypochromic and hyperchromic effect
(d) Interpret UV spectra
(e) Describe application of UV in chemistry

6.2.1 Electronic Energy State

Electronic energy state of a diatomic molecule is represented by a potential energy curve
which is a plot of potential energy against internuclear distance, ground state and excited
electronic states are shown by curves in Fig. 1.1. Each electronic state has a series of
vibrational energy states (rotational levels are not shown).

Normally transitions occur from the lowest vibrational level of a ground electronic state to
different vibrational levels of excited electronic state. Electronic transition in a molecule
takes place so rapidly in comparison to vibrational motion that atoms in the molecule do not
have time to change their positions and hence there is no change in internuclear distance
during transition. All transitions occur vertically since the value of does not change.
(Frank-Condon principle)

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 Figure 1.1: Digrammatic representation of Potential Energy of a diatomic molecule showing: (A) Potential
Energy-Nuclear Separation Curves; (B) Relationship between Electronic Transitions and Absorption
Curves

Here it is important to mention that all transitions do not occur with the same probability and
that too depends on change in the spin of electron during excitation. Transitions in which
spin of electron changes are called spin forbidden transitions and transitions in which electron
spin is the same in the initial and the final stage are called spin allowed transitions.
Forbidden transitions often occur but their probabilities will be low. The types of forbidden
and allowed transitions have been summarized by selection rules which give the conditions
for the probability of a particular transition. This selection rule is generally expressed a
∆1=±1 and is called Laporate Rule, after the name of its discoverer. A consequence of this
rule is that although s p, p d and d f transitions are allowed, d d transitions are forbidden
since all the d orbitals have the same l value and ∆1=0 for a d transition. If they do occur,
they are weak.

This fact may be explained further by considering the dipole moment during an electronic
distribution. There will be no change in the dipole if there is symmetrical electronic
redistribution and this type of transition is forbidden, for example transition is not
allowed since it involves no transition dipole moment’ whereas transition is allowed
because it corresponds to an unsymmetrical movement of charge. It is the transition dipole
moment associated with redistribution of charge which is responsible for the electronic
transition s p transition is allowed but s s transition is forbidden since it has zero transition
dipole.

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E-tivity -6.2.1 UV spectroscopy.

Numbering, pacing and 6.2.1

sequencing
Title UV spectroscopy.
Purpose The purpose of this e-tivity is to enable you to describe
UV spectroscopy
Brief summary of overall Read the materials on these links
task https://www.youtube.com/watch?v=8ELMSzwU1cs&a
b_channel=ManishaTanwer

https://www.youtube.com/watch?v=Qsze0KaART4&a
b_channel=ChrisAmbidge

Spark

Individua task a) Describe types of electronic transitions in UV

spectrocopy

Interaction begins 1. Post two themes that are in UV spectra

E-moderator interventions
2. Provide positive and constructive feedback on the
team learners ‘views and ideas. Do this on the
discussion forum 1.2.4
1. Ensure that learners are focused on the contents
and context of discussion.
2. Stimulate further learning and generation of new
ideas.
3. Provide feedback on the learning progress.
4. Round-up the e-tivity

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 Schedule and time This task should take two hours
Next Type of Electronic transitions

6.2.2 Type of Electronic transitions

So far we have discussed the transition of an electron from a given ground level to a given
excited level. But in a molecule, there are different types of electrons with different energies
in ground state. These different electrons ( ) can be excited to higher energy states
giving rise to many possible excited states. Thus many transitions from the ground state to
different excited state are possible in one molecule. The energy levels of different types of
electrons and allowed transitions are given below (Fig. 1.2).

Figure 1.2. Energy of molecular orbitals andelectronic transitions

Allowed transitions are:

are bonding electrons and are their antibonding electrons. Non-bonding

electrons n do not form bonds and hence do not have their antbonding electrons.

Let us discuss these transitions in some detail.

1. transitions
This type of transition occurs in compounds which are saturated with no lone pair of
electrons, i.e, alkanes. The energy required for this type of transitions is very high,
therefore, the spectrum appears in far UV region. This explains why most saturated

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 hydrocarbons are colourless. For ethane λmax is 135 mµ which is for UV region.

2. transitions
This type of transition occurs in saturated compounds with lone pair of electrons, in
addition to electron. This transition requires less energy than transition,
therefore, spectra appear in UV or visible region. In methanol two transitions are
possible, and with λmax 150 and 183 mµ. The shorter wavelength is
due to transition and longer wavelength is due to transition.

3. transitions
This transition occurs with unsaturated compound containing multiple bond or
aromatic ring. This transition is of intermediate energy λmax for ethylene is 175mµ.
Benzene absorbs at 184, 204 and 254mµ. All are ……transitions. The sharp band
near 184mµ result from allowed transition whereas the weaker bands near 204 and
254 mµ results from forbidden transitions.

4. transitions
It occurs in unsaturated compounds with lone pair of electrons. This transition is of
lowest energy. Aldehydes and ketones are examples of this type of transitions.

Electronic transitions in some compounds are given below:

TABLE 1.1

Compound Transition xmax(mµ)

methane 125
ethane 135
ethylene 165
acetylene 178
methyl chloride 173
water 167
acetone 188
280

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 150
benzene 204
180
254
aniline 230
280
nitrobenzene 270
toluene 262

6.2.3 Some definitions

1. Chromophores
Chromophores are defined as a group of atoms, having electron. They are
responsible for the absorption band.
Examples are: - , - = -, . Analysis of spectrum is
done on the basis of these chromophores. These chromophores act as a functional
group, having characteristic absorptions. A list of absorption of some chromorphoric
group is given in Table 5.2.

Chromophore Compound λmax (m )

εmax

Elthylene 170 15,800

Cyclohexene 184 7,600

185 2,000
222 126

Acetalehyde 277 (n 6
290 (n 16
279 (n 15
O

H
Aceticacid 208 60
H3C O

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Actonitrile 160 Weak

N=N Azomethane 340 5

O
Acetamide 178 9,500
R NH2

220 63

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 O
Acetyl chloride 220 100
R Cl

2. Auxochromes
Auxochromes are defined as group of atoms which do not give rise to absorption band
on its own, but are able to change the absorption maxima when they are attached to
the chromophores. Typical groups are OH, NH2, CI, Br, I, SH, CH3. λmax for benzene
is 255 whereas for aniline is 280 mμ because of H2 group.

3. Bathochromic shift or red shift

Shift of band towards longer wavelength is called bathochromic shift or red shift.

4. Hypsochromic shift or blue shift

Shift of band towards shorter wavelength is called, hypsochromic or blue shift. These
two shifts are the result of substitution and solvent.

5. Hypochromic effect
Decrease in the intensity of band is called hypochromic effect.

6. Hyperchromic effect
Increase in the intensity of band is called hyperchromic effect.

7. Conjugation
If two chromophoric groups are separated by a single bond (conjugation), much
change in the spectrum is observed. When chromophores are in conjugation the value
of λ increases. Conjugation lowers the energy required for transition and band moves
to longer wavelength as given below:

Simple chromophoric λmax Conjugated system λmax

system (mµ) (mµ)

CH2 CH2 180 CH2 CH CH= CH2 217

CH = CH 173 CH C CH= CH2 219
(CH3)2C=0 187 (CH3)2C=CH C=0 225

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 As the number of altering single and double band increases the band moves to longer
and longer wavelength absorption moves into visible region so that the compound
appears coloured. When one of the hydrogen atoms in butadiene is replaced by an
alkyl group the value of λmax increases as seen below.

CH2 CH CH= CH2

RCH=CH-CH=CH2
RCH=CH-CH=CnR

This increase is due to attachment of auxochrome alkyl group. When an auxochrome is

attached to carbon-carbon double bond it causes a shift in the absorption to longer
wavelength. Some example are given below

Auxochrome Unsubstituted λmax Substituted λmax

chromophore chromophore
(mµ) (mµ)

CI CH2 CH2 175 CH2 CHC1 185

OR CH3CH=CHCOOH 204 MeC(CH30) 234

=CHCOOH

If there are enough double bonds in conjugation the value of λmax is shifted to longer
wavelength visible region and the compound will be coloured. For example in polycylic
aromatic hydrocarbons, as the number of rings increases the value of λmax increases (Table
(1.3) Gradual increase in λmax explains the colour of the compound. Benzene is colourless
whereas hexacene is green. The lutein, which gives egg yolk its yellow colour is a compound
with nine alternating single and double bonds as the compound lycopene which is responsible
for the red colour of tomato, has eleven double bonds in conjugation.

Table 1.3
Compound λmax (mµ) λmax (mµ)

C=C-C=C 47
Benzene 203 260
C=C-C=C-C=C 258
Napthalene 320 280

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 C=C-C=C-C=C-C=C 310
Anthracene 370 375
Nephthacene 460 450
Pentacene 580 575
Hexacene 600

FFECT OF SOLVENT ON λmax

The position and intensity of spectra is highly dependent on the nature of solvent. As far as
possible one should use non-polar solvent because it produces little change in the position of
bands. In hydroxylic solvent the structure gets completely blurred. Studies of solvent effect
have been made both in n and in transitions. The wavelength of n bands
are generally found to decrease (blue shift) with the increase in polarity of solvents as seen
below a characteristic of n transition.

Solvent hexane CHC

λmax 279

Polar solvents generally shift the transition to longer wavelength (red shift). Thus
solvent studies is an important criteria to distinguish and transition.

6.2.4 Applications of UV spectroscopy

1. Determination of molecular weight

Determination of molecular weight is based on the fact that when a substance forms a
derivative with a reagent which has a characteristic band at wavelength, where the substance
does not absorb, the value of is nearly the same as that of reagent.

2. Identification of a Compound
Identification of a compound can be done by comparing its spectrum with a spectrum of
standard sample but the identity of compound is confirmed with the help of information so
obtained in conjugation with other evidences. However UV spectroscopy is of little use for
identification purposes because many molecule give exactly similar spectra although they
may slightly differ in their structure.

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3. Study of cis and trans isomcrism
Trans isomers have higher values of…….. that cis isomers. In case of cis form due to
proximity of the two benzene rings there will be steric hinderance resulting in decreased
resonance whereas trans isomers are elongated. Greater the hinderance shorter the
wavelength. UV spectra of cis and trans stilbene illustrate this fact.

4. Study of Tautomerism
Let us consider the tatutomeric equilibrium of acetoacetic ester where the equilibrium is
Enol form shows a high intensity band due to conjugated double bond around 245mu.
Ketoform shows weak band around 275mu (n * transition) characteristic of an isolated
carbonyl group. Intensity of enol band in various solvents have been studied and it is found
that the position of proton donor solvent decrease the magnitude of enolization.

λmax % enol
Hexane 244 57
Ether 244 32
alcohol 266 12

5. Study of Hydrogen bonding

Intramolecular hydrogen bonding has a pronounced effect on UV whereas intermolecular
hydrogen bonding has a small effect. Intramolecular hydrogen bonding produces
bathochromic shift which leads to absorption at longer wavelength.

Water forms a stronger hydrogen bond that ethanol, it takes more energy to break the
hydrogen bond and greater overall energy to promote the lone pair electron to the excited
state and a shift to shorter wavelength occurs. Compounds forming intramolecular hydrogen
bonding undergo a blueshift i.e., shift to shorter wavelength.

6. Study of Transition metal complexes

The bands in transition metal complexes arise due to d-d transition. The energy difference
between these two d states is so small that even absorption of visible light is sufficient to
cause excitation of an electron from a lower to higher d level. This is the cause of colour of

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transition metal complexes. The frequency of first d-d transition band directly gives the
value of 10Dq, where 10 Dq is called splitting parameter. The value of Dq can be known
experimentally from the spectrum of the complex.

7. Study of reaction kinetics

UV spectroscopy can be used in the study of rate of chemical reactions. Consider the
dehydration of n hydroxyl ketone as an example. The product will give a strong band in the
region 225-240 mµ and the reactant gives a weak band in the 200-300 mµ region. The rate of
reaction can be studied by observing the increase in intensity of the 225-240 mµ band with
time.

8 Calculation of dissociation energy

Dissociation energy may be determined from the spectrum. It is calculated from the
wavelength that separates the discontinuous part of spectrum resulting from the dissociation
of molecule into two parts.

When the spectrum is examined, it is found that at one end of the spectrum the distance of
separation of lines becomes smaller and smaller until at a given position the line spectrum
terminates and a space of continuum starts. The position of the limit where the lines end
gives the wavelength of radiation necessary for dissociation of molecule. The spectral
calculation of dissociation energy can be explained by Fig. 5.8
Dissociation energies Do for some diatomic molecules are given in Table 5.4.

Molecule Do(kcal/mole)
H2 103.2
O2 117.2
N2 170.2
C12 61.2
Br2 45.5
HC1 102.2
CO 256.2

9 Study of charge transfer complexes

UV spectroscopy is probably the most suitable tool for the study of charge transfer complexes
(Donor acceptor complexes). In the spectra of iodine (acceptor) and benzene (donor), a very

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intense charge transfer band is observed in a compound formed between iodine and benzene.
The absorption band for I2 occurs at about 520mu in solvent CCI4.
. 5.9. Absorption spectra of pure iodine (broken lines) showing the effect of changed
concentration of donor keeping I2 (acceptor) concentration constant.

Table 5.5
Spectroscopic and thermodynamic data on the charge transfer complexes of benzene with
several acceptors

Acceptor hvit K
(kcal) Litre mole ∆Ho t

12 98 .15 1.32 16400

Br2 87.5 1.04 - 13400
C12 103 .33 - 9090
Trinitro benzene 101 .23 1.71 .277

The data on the interaction of iodine with several donors are also available and given in Table
5.6.

Spectroscopic and thermodynamic data for few charge transfer systems.

Donor Solvent K ∆Ho Hvct
Benzene CC14 .15 1.32 98
Diethyl ether CC14 .87 4.20 115
Pyridine Heptanes 290 8.00 122
Triethyl amine Heptanes 6000 12.20 103
Dimethyl sulphide Heptanes 200 8.90 94

Effect of solvent on the position of band in pyridine-iodine system are given in Table 1.7

Table 1.7
Solvent effect in pyridine-iodine systems
Solvent D K max λmax
Chloroform 4.81 63 1669 404.5

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CC14 2.24 111 1389 418.5
Cyclohexane 2.02 126 1383 424.5
n heptane 1.92 140 1386 424.5
n hexane 1.87 127 1450 426.5

Determination of dissociation constant of acids and bases

Determination of dissociation constant of an acid or a base is based on changes in the
absorption spectra with the pH of the medium. Let us consider dissociation of an acid HB in
water as follows:-
HB + H20 H30++B-
where B- is the conjugate base. Applying the law of mass action.

Taking log on both sides

Log Ka=Log………………………………
If the pH of solution and concentration of HB and B- are measured (spectrophotometrically),
pKa can easily be calculated.

6.2.5 SOLVED PROBLEMS

1. Offer an explanation for the following variations
λmax for methane = 125 mu
λmax for ethane = 135 mu
λmax for cyclopropane = 190 mu

Here is σ transition. In methane only one transition is involved, i.e. for C-H
bond. In ethane two transitions are involved, one for C-H bond and other for C-C
bond. C-C bond transition requires less energy (longer wavelength) than that for a C-
H bond. C-C bonds in cyclopropane are not pure bonds. They partially have
bond character so transition requires still less energy (longer wavelength).

2. The UV spectrum of acetone shows three peaks of λmax 280,188 and 154mµ. What
chromophore is responsible for each transitions? What types of transitions cause
these peaks? Which peak is most intense?

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 Carbonyl chromophore is responsible. The longer wavelength 280mµ is associated
with smaller energy i.e. n transition. transition occurs 188mµ. n
transition occurs at 154 mµ. Transition having lorger εmax will give most intense
peak.

3. Explain the variation in the value of λmax for CH3X

where X-C1(173) mµ, Br (204) mµ I (258) mµ.

Here transition must be n…. On going from C1 to Br to I the n electrons are found in
higher principal energy levels. (Principal quantum numbers are 3, 4 and 5
respectively). These electron are more away from the attractive force of the nucleus
and hence can easily be excited. This is the reason, as to why absorption occurs at
higher value of λmax.

4. Explain all possible electronic transition for CH4, CH3C1 and H2C=0
(i) σ
(ii) σ
(iii) σ ,σ n and n

5. Explain why butadiene has higher λmax than ethylene? Using molecular orbital theory
relative energies are shown below:

In butadiene the excitation is from 2 to 3 i.e., highest occupied m.o. to lowest

vacant m.o. Energy difference for this transition is less than the energy difference for
for ethylene. So λmax for butadiene is greater (217 m ) than for ethylene
(170m ).

6. transitions for two compounds are given below: why these two transitions
do not absorb at the same wavelength:
While both the transitions are due to the electronic
environment of the carbonyl group is not same to the environment about the triple
bond. Thus transition requires different energy.

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7. A certain compound dissolved in hexane had a λmax =305mu when the same
compound was dissolved in ethanol λmax was 307mu. Give your reasoning.

Here is transition. Ethanol is more polar and hydrogen bonding solvent than
hexane. The transition is of lower energy in ethanol than in hexane. The shift to
longer wavelength with more polar solvent is the characteristic of transition.

8. A 1 x 10-5 molar solution of a compound has a % transmittance of 50 at λmax=280

when a 1 cm cell is used. alculate εmax.

SUPPLEMENTARY PROBLEMS
1. What would be the effect of the polarity of solvent on the value of λmax for alkenes?
[Hint: Alkenes do not have lone pairs so interaction between solute and solvent is not
possible. Hence polarity of solvent will have no effect on λmax]

2. What do you understand by singlet and triplet state of a molecule? Which state would
have lower energy and why?
[Hint: Singlet and triplet states are the result of electronic excitation with or without
change of spin. Triplet states have lower energy. Increase in multiplicity leads to
lower energy.]

3. What are the various electronic transitions that give rise to UV spectra. How is the
position of λmax affected by:
(a) Nature of solvent
(b) Conjugation of chromophoric groups

4. Explain with the help of diagram how will you utilize the phenomenon of pre-
dissociation for determining the dissociation energy of a diatomic molecule.

5. What are the usual electronic transitions observed in the UV spectrum of compounds
containing a carbonyl group. Discuss the effect of various solvents and auxochromes
on the electronic spectra of such compounds.

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6. Predict which compound in the following pairs shows an absorption maxima near the
end of UV or visible spectrum. Justify also.

(a) CH2- H= H………..

(b) p-nitrophenol and m-nitrophenol

7. State Lambert and Beers law. How would you determine the concentration of
unknown solution of K2Cr207 using UV or visible spectroscopy?

8. What is the order of energies required for the usual electronic transitions observed in
case of molecules containing carbonyl group. Discuss the effect of various solvents
and auxochromes on the electronic spectra of such molecules.

9. A compound A has the formula C11H16O. It is reduced to compound B with formula

C11H18O. Compound B has the following structure:

Diagram

The UV spectra of A showed strong band at ymax=225mu. This band was not
present in the spectrum of B. Predict the structure of A.

10. Arrange the following polyenes in order of increasing ymax.

(a) All trans CH3(CH=CH)10CH3

(b) All trans CH3(CH=CH)9CH3
(c) All trans CH3(CH=CH)8CH3
11. Predict the kind of transitions present in (a) C12 molecule (b) C=O group. Which
will be allowed and which one will be forbidden?

Ans (a) In C12 molecule the allowed transitions will be relative to

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 which is forbidden.
(b) In carbonyl group, the orbitals involved are

(i) n both weak

(ii) , both strong
12. Predict the numbers of electronic transitions in the following molecules.
Ans
(a) CH3C1
(b) CH2=CH2
(c) NO2 group n
(d) NH2 group n
(e) SO group n

alent protons and the number of NMR signals, thus observed.

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