ELECTRONIC SPECTROSCOPY

In this branch of spectroscopy, information about the molecule under

investigation are obtained from the various types electronic transitions taking place.
Depending on the types of electrons present i.e. bonding ,  electrons
and nonbonding n electrons, different types of electronic transitions occur. The term
electronic spectroscopy is used for the study of the transitions between different
electronic states which lie in visible and ultra-violet region of electromagnetic spectrum.
Electronic transitions are also accompanied by Vibrational and rotational energy
changes. The rotational energy changes produce rotational fine structure while the
vibrational energy changes produce Vibrational coarse structure in electronic spectra.
Again, in cases of the molecules containing more than one type of electrons, several
transitions may occur resulting in the formation of several bands.

Electronic Transitions

When a molecule absorbs Ultra-violet or Visible light, its electrons get promoted
from ground state to the higher excited state. During excitation an electron gets excited
from a bonding to an antibonding orbital.
Possible electronic transitions of bonding ,  electrons and nonbonding

n electrons to antibonding * and * orbitals are -

(i) * Transitions

In this type of transitions a bonding σ electron is excited to an antibonding σ*.

As the σ bonds are very strong, so this process requires very high energy. This type of
transitions requires radiation of very short wavelength.

For example, saturated hydrocarbons like methane (which has only C-H bonds,
and can only undergo σ→ σ* transitions) shows an absorbance maximum at 125 nm.
Absorption maxima due to σ→ σ* transitions are not seen in typical UV-Vis. spectra
(200 - 700 nm).
(ii) n → σ* Transitions

In this type of transitions a non-bonding n electron is excited to an antibonding σ*

orbital. These transitions usually need lesser energy than σ→ σ* transitions. They can
be initiated by light whose wavelength lies in the range 150 - 250 nm.

For example, Saturated compounds containing atoms with non-bonding electrons

i.e. lone pairs are capable of showing n→ σ* transitions. Organic compounds
undergoing this type of transitions are halides, alcohols, ethers, aldehydes, ketones,
amines etc.

The absorption maxima of such transitions depend on the electronegativity of

the atom containing the lone pair of electrons. If we observe the absorption maxima of
CH3Cl and CH3I, it can be seen that the absorption maxima of CH 3Cl is around 174 nm
while the absorption maxima of CH3I is around 260 nm. This is because chlorine being
more electronegative than iodine, it takes higher energy (lower wavelength) for exciting
the non-bonding electrons. The molar extinction co-efficient (εmax) for the molecule is
found to be higher in which the n→ σ* transition takes place readily. Thus out of CH3Cl
and CH3I, CH3I will have higher molar extinction co-efficient.

Similarly, amines absorb at higher wavelength in comparison to alcohols as

oxygen is more electronegative than nitrogen. Hence, ε max of amines are higher than the
alcohols.

(iii) π→ π* Transitions

In this type of transitions π electrons are excited to antibonding π* orbital. These

transitions require lesser energy than n→ σ* transitions and hence radiation of longer
wavelength can also initiate such transitions.

For example, molecules containing π electrons (unsaturated centres i.e. double

or triple bonds and also aromatic rings) show π → π* transitions. Organic compounds
undergoing this type of transitions are alkenes, alkynes, aldehydes, ketones, cyanides,
azo compounds etc. The introduction of alkyl groups to the unsaturated centres
increases the wavelength of absorption by 3-5 nm per alkyl group.

(iv) n→ π* Transitions

In this type of transitions non-bonding n electrons are excited to antibonding π*

orbital. This type of transitions requires least amount of energy out of all the electronic
transitions.

For example, the compounds which involves nonbonding n electrons and π

electrons show both π → π* and n→ π* transitions. Compounds undergoing this type
of transitions are Carbonyl compounds, Nitriles, C=S, N=N, etc. The low energy n→ π*
transition occur at longer wavelength than π → π* transition. Usually shorter
wavelength transitions are more intense.

The energy order for various transitions can be shown as –

σ→ σ* > n→ σ* > π → π* > n→ π*

Various types of electronic transitions occurring in ultra-violet and visible

spectroscopy are shown in Figure 3.1.

Fig.3.1 Types of electronic transitions

Selection Rule for Electronic Transitions

There are mainly two selection rules which should be followed for an electronic
transition to occur. These are -
Laporte Selection Rule

According to this rule, the only allowed transitions are those which involve a
change in parity i.e. gerade → ungerade (g→ u) and ungerade → gerade (u→ g) are
allowed while gerade→ gerade (g→ g) and ungerade→ ungerade (u→ u) are forbidden.

Spin Selection Rule

According to this rule, the only allowed transitions are those which involve no
change in spin state i.e. transitions from singlet → singlet and triplet → triplet are
allowed while transitions from singlet → triplet and triplet → singlet are forbidden.

Born-Oppenheimer Approximation

This approximation was proposed in 1927, in the early period of quantum

mechanics, by Max Born and J. Robert Oppenheimer and is still indispensable in
quantum chemistry.

In this approximation (Born-Oppenheimer approximation), it is assumed that

the motion of nucleus and electrons in a molecule can be separated. Mathematically,
the total wave function (Ψtotal) can be written as a product of electronic and nuclear
components i.e.

Ψtotal = Ψelectronic X Ψnuclear

The complication that arisen while solving for the total wave function, was simplified
by Born and Oppenheimer in their approximation. In Born-Oppenheimer approximation
two simple steps were used to solve for the Ψtotal.

In the first step, nuclei are fixed at a certain configuration (usually equilibrium
configuration) and then the electronic Schrödinger equation is solved to get the
wavefunction Ψelectronic which depends only on electrons.

In the second step, the nuclear equation is solved to get the wavefunction Ψnuclear
which depends only on nuclei.

Application of Born-Oppenheimer approximation can be discussed taking benzene

as an example. Benzene contains 12 nuclei and 42 electrons. It has a total of 162
variables (12x3=36 for the nuclei and 42x3=126 for the electrons). In order to obtain the
energy and wavefunction of this molecule, it is necessary to solve the time independent
Schrodinger equation. For benzene, this equation is a partial differential eigen value
equation in 162 variables that contain the spatial coordinates of the electrons and the
nuclei. During solution, in the first step, the nuclei are fixed in equilibrium configuration
and then the electronic wavefunction is solved (Ψelectronic). As the nuclei are fixed, so, the
wavefunction depends only on 126 electronic coordinates. In the second step only the
nuclei is considered, so, the wavefunction depends only on 36 nuclear coordinates. In
this way the solution was made simpler in Born-Oppenheimer approximation.

This approximation is an important tool for quantum chemistry as well as molecular

spectroscopy. Under this approximation, it is quite easier to get the wavefunctions for
large molecules, on the otherhand, if this approximation is not considered then only the
wavefunction of the lightest molecule i.e. H2 can be solved. The success of the BO
approximation is due to the large difference between the masses of the nuclei and the
electrons.

Vibrational Coarse Structure

The electronic, Vibrational and rotational energies of a molecule are completely

independent of each other and hence the total energy of a molecule may be given as –

E total = E electronic + E vibration + E rotation J

In terms of wave numbers, the above equation may be written as –

ε total = ε electronic + ε vibration + ε rotation cm-1 ………. (3.1)

Thus, a change in total energy of the molecule may be written as –

∆ ε total = ∆ ε electronic + ∆ ε vibration + ∆ ε rotation cm-1

The approximate magnitude of changes generated by the electronic, Vibrational

and rotational energies are –

∆ε electronic ≈ ∆ ε vibration X 103 ≈ ∆ ε rotation X 106

 From the above magnitudes, it can be mentioned here that the Vibrational
changes will produce a coarse structure while the rotational changes will produce a
fine structure in the spectra of electronic transitions. Thus, in order to understand the
coarse structure in the spectra of electronic transitions, it is important to ignore the
rotational changes. Hence, without taking the rotational changes into consideration
equation (1), may be written as –

ε total = ε electronic + ε vibration cm-1 …………………. (3.2)

Again the pattern of the Vibrational energy levels can be given as –

Where v = 0,1,2,3 ……..

is the oscillation frequency expressed in wavenumbers also called

Vibrational wavenumber

Xe is the corresponding anharmonicity constant

Combining equation (3.2) and (3.3), we can write,

For two arbitrary values of ε electronic (ε” electronic and ε’ electronic) the Vibrational
coarse structure of the band formed during electronic absorption from the ground state
(v” = 0) to higher states (v’) are shown in Figure 3.2. From the figure, it is clear that the
spacing between the upper Vibrational levels are smaller than that between the lower,
this is because an excited electronic state generally corresponds to a weaker bond in a

molecule and hence a smaller Vibrational wavenumber ( ). The spacing between the
lines decreases with increase in frequency, this is due to anharmonicity of the upper
state vibration which causes the excited Vibrational levels to converge.
 Conventionally, the transitions are represented as (v’,v”) i.e. (0,0),(1,0), (2,0) etc.
under high resolution, the lines formed from different transitions are seen as separate
lines, however, under low resolution, a set of lines appear as diffused and broad and
hence such a set is called a band. Moreover, in a set of lines as the values of v’
increases by one unit, so, such a set of lines is also called a v’ progression.

The study of a band spectrum enables one to get the values of Vibrational
wavenumber and anharmonicity constant for both the ground as well as excited
electronic state and also the separation between the electronic states.

Fig.3.2 Vibrational coarse structure of the band formed during electronic absorption

Franck-Condon Principle

The Franck-Condon Principle describes the intensities of vibronic transitions or

the absorption or emission of a photon. Vibronic transitions are the simultaneous
changes in electronic and vibrational energy levels of a molecule due to the absorption
or emission of a photon of the appropriate energy. During an electronic transition, a
change from one vibrational energy level to another will be more likely to take place if
the two vibrational wave functions overlap more significantly.

As the mass of the nuclei are quite larger than that of the electrons and electronic
transitions take place quite faster, so, the nuclear configuration almost remains same
during the transition. Thus, the Franck-Condon Principle may be stated as –

An electronic transition takes place so rapidly that a molecule undergoing

vibration does not change its internuclear distance significantly during the transition.

Moreover, it may be mentioned here that the most intense vibronic transition is
one in which the excited Vibrational state lies vertically above the ground Vibrational
state. However, transitions to the other Vibrational levels also occur, but in that cases
the intensity of the transitions are found to be quite lower. To understand this fact, let us
consider four cases –

Case I

In this case the upper electronic state (ε’) is having slightly less equilibrium
internuclear distance (re) than the lower
electronic state (ε”). Here the transition
that occurs vertically is from (v” =0) to
(v’=2). So, the most intense line will be
(2,0), because in this transition the
internuclear distance does not change
(Figure 3.3).

Fig.3.3 Transition in which upper state internuclear distance is less than the lower state
Case II

In this case the upper electronic state (ε’) is having the same equilibrium
internuclear distance (re) as the lower electronic state (ε”). Here the transition that
occurs vertically is from (v” =0) to (v’=0). So, the most intense line will be (0,0), because
in this transition the internuclear distance does not change (Figure 3.4).

Fig.3.4 Transition in which the internuclear distances are same for both upper and
lower state

Case III

In this case the upper electronic state (ε’) is having slightly more equilibrium
internuclear distance (re) than the lower electronic state (ε”). Here the transition that
occurs vertically is from (v” =0) to (v’=2). So, the most intense line will be (2,0), because
in this transition the internuclear distance does not change (Figure 3.5).

Fig.3.5 Transition in which upper state internuclear distance is greater than the lower
state

Case IV

In this case the upper electronic state (ε’) is having considerably more equilibrium
internuclear distance (re) than the lower electronic state (ε”). In this case the observation
is somewhat different than that already discussed in the above three cases. Here the
Vibrational level to which a transition takes place has a quite high v’ value (to get a
vertical transition). Moreover, in this case transitions may take place to a state in which
the excited molecule has energy in excess of its own dissociation energy. As a result
the molecule will dissociate into its constituent atoms without any vibrations. Since the
atoms formed may take up any value of kinetic energy, so, transitions are not quantized
and results in the formation of a continuum (Figure 3.6).

Fig.3.6 Transition in which upper state internuclear distance is considerably greater than
the lower state

Problem 3.1: Using the Franck-Condon principle, explain why the intensities of the
vibrational lines associated with electronic transitions differ. [GU 2016]
Problem 3.2: Discuss Franck-Condon principle to explain intensities of vibronic
transitions due to absorption or emission of a photon of appropriate energy. [GU 2014]

Problem 3.3: State and explain Franck-Condon principle. Discuss how this principle is
applicable to explain the intensity distribution of vibrational bands in electronic transition.
[GU 2013]

Structure Elucidation by Electronic Spectroscopy

Chromophore

When an electron jumps from a ground state to an excited state, it absorbs

radiation of appropriate wavelength. But it is important to note that the nuclei associated
with the electrons, play an important role in determining the wavelength of absorbed
radiation. The nuclei of an atom determine the strength with which the electrons are
bound and hence influence the energy spacing between ground and excited states.
Hence, the characteristic energy of a transition and the wavelength of radiation
absorbed are properties of a group of atoms rather than that of electrons. The group of
atoms responsible for the absorption is called a chromophore.

Thus, the isolated covalently bonded group that shows a characteristic

absorption in the ultra-violet or visible region is known as chromophore.

Examples of some chromophores with transition and maximum wavelength of

absorption are shown in Table 3.1.

Table 3.1 Chromophores with type of transition and absorption Maxima

Absorption
Chromophore Transition
Maxima, λmax (nm)

R2-C=C-R2 π→π* 175

R-C≡C-R π→π* 170

n→π* 285
R2C=O
π→π* 188
 n→π* 290
R-CHO
π→π* 190

R-NO2 n→π* 271

R-COOH n→π* 205

R-CONH2 n→π* 210

R-COOR n→π* 205

R- C≡N n→π* 160

R-N=N-R n→π* 340

Auxochrome

The position as well as the intensity of the absorption band of a chromophore can
be changed by the attachment of certain groups in place of hydrogen to a basic
chromophore. Such substituents may not give rise to the absorption, but their presence
changes the position and intensity of the absorption band.
Thus, an auxochrome may be defined as any substituent or group which itself
doesnot absorb, but its attachment to the chromophore, increases the intensity of
absorption and shifts the absorption band to the longer wavelength.
Some examples of auxochromes include –OH, -R, -OR, -X, -NH2 etc.
The effect of the auxochrome is due to its ability to extend the conjugation of the
chromophore by the sharing of non-bonding electrons. Hence, by the attachment of
auxochrome to the basic chromophore, a new chromophore results which has a
different value of the absorption maxima as well as the extinction co-efficient. For
example , benzene shows an absorption maxima at 255 nm , while aniline absorbs at
280 nm. So, here amino group act as an auxochrome.

Bathochromic Shift (Red Shift)

The shift of the absorption maxima towards lower energy or longer wavelength
due to presence of an auxochrome or by the change of solvent polarity is known as
bathochromic shift or red shift.
 The n→π* transition of carbonyl compounds show bathochromic shift due to
decrease in solvent polarity.

Hypsochromic Shift (Blue Shift)

The shift of the absorption maxima towards higher energy or shorter wavelength
due to removal of conjugation or by the change of solvent polarity is known as
hypsochromic shift or blue shift.
In aniline, the lone pair of electron shows conjugation with the π – electrons of
the benzene ring and hence has absorption maxima at 280 nm. But in acidic solution,
due to the formation of anilinium ion, the lone pair of electron on nitrogen is no longer
available and as a result the conjugation is lost. Hence, anilinium ion shows absorption
maxima at shorter wavelength of 200 nm showing a blue shift.

Hyperchromic Effect
The effect due to which the intensity of the absorption band of a chromophore
increases due the presence of an auxochrome is known as hyperchromic effect.

Hypochromic Effect
The effect due to which the intensity of the absorption band of a chromophore
decreases is known as hypochromic effect.

Problem 3.4: Define auxochrome. What do you mean by red shift and blue shift of
absorption maximum ? [GU 2016]

Problem 3.5: “The absorption at longer wavelength in electronic spectroscopy is due to

the combination of a chromophore and an auxochrome group.” Describe what do you
mean by chromophore and auxochrome. Also explain briefly red shift and blue shift.
[GU 2015]
Absorption due to ethylene chromophore

Woodward’s Rules

Woodward gave some empirical rules to calculate the λ max for conjugated dienes,
trienes and polyenes. According to Woodward, some basic value is assigned to the
parent compound and the increments made by each substituent is added to it. The
values of the parent compound as well as various increments for dienes are shown in
Table 3.2.

Table 3.2: Values of the parent compound as well as various increments for dienes.

Class Homoannular Heteroannular

(cisoid) (λ nm) (transoid) (λ nm)

Parent 253 214

Increments:

Double bond extending conjugation 30 30

Alkyl substituent or ring residue 5 5

Exocyclic double bond 5 5

Auxochrome:

-OR 6 6

-Cl, -Br 5 5

-OCOCH3 0 0

-NR2 60 60

NB:
(i) A heteroannular diene means that the two double bonds in conjugation are
present in different rings.
(ii) A homoannular diene means that the two double bonds in conjugation are
present in same ring.
(iii) A double bond which lies at the junction of two rings is known as an exocyclic
double bond. If a double bond connects two rings then it is considered as two
exocyclic bonds.

Problem 3.6: Calculate the λmax for the following compounds as per Woodward rule –

ii.
i.

H3CH2CO

iv.
iii.
Solution:

(i) Heteroannular Diene (Transoid) = 214 nm

Ring Residue – (3 X 5) = 15 nm

Exocyclic Double Bond = 5 nm

______________________________________

Calculated (λmax) = 234 nm

Observed (λmax) = 235 nm

(ii) Heteroannular Diene (Transoid) = 214 nm

Ring Residue – (3 X 5) = 15 nm

Exocyclic Double Bond = 5 nm

-OCH2CH3 (-OR) = 6 nm
_______________________________________

Calculated (λmax) = 240 nm

Observed (λmax) = 241 nm

(iii) Transoid = 214 nm

Observed (λmax) = 217 nm

(iv) Transoid = 214 nm

Alkyl groups (3X5) = 15 nm

_____________________________________

Calculated (λmax) = 229 nm

Observed (λmax) = 228 nm

Problem 3.7 : Calculate the λmax for the following compounds as per Woodward rule –

ii.
i.

H3CCOO

COOH

Solution

(i) Homoannular Diene (Cisoid) = 253 nm

Ring Residue – (5 X 5) = 25 nm

Exocyclic Double Bond -(3X5) = 15 nm

Double bond extending Conjugation - (2 X 30) = 60 nm

_____________________________________________
Calculated (λmax) = 353 nm

Observed (λmax) = 355 nm

(ii) Homoannular Diene (Cisoid) = 253 nm

Ring Residue – (3 X 5) = 15 nm

Alkyl Substituent = 5 nm

Exocyclic Double Bond - = 5 nm

_____________________________________________

Calculated (λmax) = 278 nm

Observed (λmax) = 275 nm

The values of the parent compound as well as various increments for enones are
shown in Table 3.3.
Table 3.3: Values of the parent compound as well as various increments for enones.

Six membered ring Five membered Acyclic dienone

Class or acyclic parent ring parent enone
enone (λ nm) (λ nm) (λ nm)

Parent 215 202 245

Increments

Double bond extending

30 30 30
conjugation

α 10 10 10
Alkyl substituent or
β 12 12 12
ring residue
γ and
18 18 18
higher

Exocyclic double bond 5 5 5

Auxochrome
α 35 35 35

β 30 30 30
-OR
γ 17 17 17

δ 31 31 31

α 15 15 15
-Cl,
β 12 12 12

α 25 25 25
-Br
β 30 30 30

α 35 35 35
-OH β 30 30 30

δ 50 50 50

-OCOCH3 α, β, δ 6 6 6
 -NR2 β 95 95 95

Homocyclic diene component 39 39 39

NB. The values are taken from spectroscopy,Lampman,Pavia,Kriz,Vyvyan,4th edition

Problem 3.8 : Calculate the λmax for the following compounds as per Woodward rule –

O O
ii.
i.

O
iii. iv.
GU,2015

Solution

i. Acyclic enone = 215 nm

Alkyl group at α position(1X10) = 10 nm

Alkyl group at β position (2X12) = 24 nm

Calculated ((λmax) = 249 nm

 ii. Six membered enone = 215 nm

Double extending conjugation = 30 nm

Homocyclic diene = 39 nm

Alkyl group at δ position(1X 18) = 18 nm

Calculated ((λmax) = 302 nm

iii. Five membered enone = 202 nm

Ring residue at β position (2X12) = 24 nm

Exocyclic double bond = 5 nm

Alkyl group at δ position(1X 18) = 18 nm

Calculated ((λmax) = 231 nm

iv. Five membered enone = 202 nm

Alkyl group at β position (1X12) = 12 nm

Alkyl group at γ position (1X18) = 18 nm

Exocyclic double bond = 5 nm

Double extending conjugation = 30 nm

Ring residue at δ position(1X 18) = 18 nm

Calculated ((λmax) = 285 nm

Electronic Transitions in conjugated polyenes from particle in a box model

The energy levels for free particles restricted to move in a 1D box are given by –

En = n2h2/8ma2
Where n=1,2,3,……..

a = length of the potential box

m = mass of electron

h = Planck’s constant

When an electron from the highest filled energy level with quantum number
n = N/2 is excited to the next higher level with quantum number n’ = N/2 + 1 , energy is
absorbed. The difference in energy between these two levels is given as –

∆E = h2/8ma2 [n’2-n2]

or ∆E = h2/8ma2 [ (N/2 + 1)2 – (N/2)2]

which on simplification gives,

∆E = h2/8ma2 [ N + 1]

Thus, the absorption wavelength is given by,

∆E = hν where ν = frequency of radiation

or ∆E = hc/λ where c = velocity of light, λ = wavelength of radiation

or λ = hc/∆E

or λ = hc 8ma2 / h2 [ N + 1]

or λ = 8mca2 / h [ N + 1] …………………………………… (3.1)

In the above equation, the length of the potential box is not the length of the
carbon chain but is taken as the length of the carbon chain plus one extra bond length
on each side of the chain, i.e.

a = (N -1+2) l where l = carbon- carbon bond length

or a = (N + 1) l
Putting the value of a in (i), we get

λ = 8 m c [(N + 1) l] 2 / h [ N + 1]

or λ = 8 m c (N + 1) l 2 / h

Which is the wavelength of absorption of conjugated polyene.

NB: For a completely filled conjugated system, the number of π MO’s is even. Hence in
the ground state of the system the quantum number of the highest filled MO will be N/2,
where N is the number of π electrons (or the number of carbon atoms involved).

Effects of Solvents on Electronic Transition

For the analysis, using ultraviolet spectroscopy, it is very important to choose a

suitable solvent. The position as well as intensity of absorption maxima is shifted for a
particular chromophore by changing the solvent polarity.
A good solvent should show the following characteristics –
Firstly, it should not absorb ultraviolet radiation in the same region as the
substance whose spectrum is being studied. Normally, the solvents that donot contain
conjugated systems are suitable for this study.
Secondly, it should show fine structure in absorption band. Normally, the fine
structure in the absorption band is observed, when the spectrum of the sample is taken
in non-polar solvent, as in non-polar solvent the solute doesnot form hydrogen bond
with the solvent. But in polar solvent due to the formation of hydrogen bonding between
solute and solvent, the fine structure may disappear.
Thirdly, it should have the ability to influence the wavelength of ultraviolet
radiation that will be absorbed via stabilization of either the ground or the excited state.
For a particular chromophore, it is possible to change the position as well as
intensity of absorption maxima by changing the polarity of the solvent. But there is no
any appreciable shift observed on the absorption maxima for non-polar compounds with
change in solvent polarity.
Usually, polar solvents form hydrogen bonds readily with the ground states of the
solute (polar molecules) in comparison to their excited states. In this case, polar
solvents increase the energies of electronic transitions in the molecules and as a result
the n→π * type of transitions shift to shorter wavelengths. For example, the absorption
maxima for acetone in hexane is observed at 279 nm, while in water it is observed at
264 nm.
On the other hand, in some cases polar solvents form hydrogen bonds readily
with the excited states of the solute in comparison to their ground states. In this case,
polar solvents decrease the energies of electronic transitions in the molecules and as a
result the π→π * type of transitions shift to longer wavelengths. In such case, the
absorption maxima will be more in ethanol than in hexane. In case of alcohols and
amines formation of hydrogen bonding takes place with solvent molecules. Absorptions
in this case occur due to the presence of non-bonding electrons on the heteroatoms
(n→σ* transition) and thus transition requires greater energy, thereby shifting the
absorption maxima to shorter wavelengths.
The shift in the n→π * transitions for acetone in various solvents with change
in solvent polarity is shown in Table 3.4.
For spectral analysis, usually a dilute solution of the sample is prepared. A 95%
ethanol is most commonly used as solvent for such spectral analysis.
Thus, it can be concluded that increase in solvent polarity shifts the absorption
maxima towards shorter wavelength for n→π * and n→σ* transition while to longer
wavelength for π→π *.transition.

Table 3.4: Shift in the n→π * transitions for acetone in various solvents with change in
solvent polarity.
Solvent λmax (nm)
H2O 264.5
CH3OH 270
C2H5OH 272
CHCl3 277
C6H14 279
Quantitative Estimation by Spectrophotometry
Spectrophotometric analysis is generally used whenever the sample is coloured.
Substances like dichromate, permanganate, cupric, ferric ions etc. can be analyzed
directly as such without chemical reactions. As most of the ions are colourless, these
are made to react with suitable reagents to form coloured solutions which are then put
into analysis. The reagent should be selected such that it reacts with only one ion. It
eliminates interference due to the presence of other ions in solution.
Since Beer’s law shows variation it cannot be directly applied for analytical
problems. The difficulty can be removed by plotting calibration curve between the
absorbance and the sample concentration used for preparing calibration curves. For
preparing calibration curves a series of standard solutions are prepared. The
spectrophotometer is set at that wavelength where the absorption is maximum. This
value can be known from the curve between concentration (moles per litre) against
absorbance or optical density. After this the absorbance of each solution is measured
and then plotted against the concentration of the solution to get a calibration curve.
For measuring the concentration of the unknown solution the absorbance is
measured at the wavelength as used for the calibration curve. After this the
concentration of the unknown solution can be measured from the calibration curve by
observing the value of concentration against the absorbance of the solution. The use of
calibration curves is the normal procedure for the quantitative application of
spectrophotometry.
 EXERCISE

3.1 Explain why absorption maximum (λmax) of CH3Cl is around 174 nm while that of
CH3I is around 260 nm?

3.2 Aniline shows an absorption maximum at 280 nm. What type of change in the
absorption maxima is observed if it is studied in acidic solution?
3.3 Discuss the types of electronic transitions, taking an example in each case.

3.4 If the upper electronic state (ε’) is having the same equilibrium internuclear distance
(re) as the lower electronic state (ε”), then at what point the most intense line will be
observed?

3.5 Explain taking an example, how Born-Oppenheimer approximation made it simpler

to solve the wavefunction of a system?

3.6 Explain why in case of transitions in which upper state internuclear distance is
considerably greater than the lower state, a continuum is observed.

3.7 Derive an expression for the wavelength of absorption of conjugated polyene.

3.8 Discuss how a polar solvent affects the λmax values of π→π * and n→π *
transition. [GU 2016]
3.9 What are the effects of polarity of the solvent on (i) σ →σ* , (ii) π→π * , (iii) n→π *
and (iv) n→σ* transitions ? Show with a diagram the relative frequencies of these
electronic transitions. [GU 2013]