Effect of solvent

MAHENDRA G S
M.Pharm
 A solvent is a liquid that dissolves another solid,
liquid, or gaseous solute, resulting in a solution at
specified temperature.

Solvents can be broadly classified into two categories:

Polar
Non-Polar.
A drug may show varied spectrum at particular wavelength
in one particular condition but shall absorb partially at the
same wavelength in another conditions.

These appeared changes in the spectrum are exclusively due

to various characteristic features namely-
1.Nature of solvent
2.Nature of absorption band
3.Nature of the solute
 A) EFFECT OF SOLVENT:

 The solvent exerts a profound influence on the quality and

shape of spectrum.

 The absorption spectrum of pharmaceutical substance

depends practically upon the solvent that has been employed to
solubilize the substance.

A drug may absorb a maximum radiation energy at particular

wavelength in one solvent but shall absorb partially at the same
wavelength in another solvent.

Eg: acetone in n-hexane λ max at 279nm.

Acetone in water λ max at 264.5nm.
NATURE OF SOLVENT:

 Most commonly used solvent is 95% ethanol. It is best

solvent as-

1. It is cheap
2. Has good dissolving power
3. Does not absorbs radiations above 210nm.

 In choosing a solvent, consideration must be given not only

to its transparency, but also to its possible effects on absorbing
system.

 There are other solvents which are transparent above

210nm.

 Benzene, chloroform , carbon tetrachloride cannot be used

because they absorb in the range of 240-280 nm.
Common solvents used in recording UV-spectra

Solvent wavelength (nm)

Water 205
Methanol 210
Ethanol 210
Ether 210
Cyclohexane 210
Dichloroethane 220
CHOICE OF SOLVENT:
A suitable solvent for UV-spectroscopy should meet the
following requirements.

It should not itself absorb radiations in the region under

investigation.

It should be less polar so that it has minimum interaction

with the solute molecules.
1.Polarity : plays an important role in the position and
intensity of absorption maximum of a particular
chromophore.

a) In case of non-polar solvents for eg. Iodine solution

(purple colour) the absorption maxima occurs at almost the
same wavelength as in iodine vapour(5180 A0)

b) In case of polar solvents , a brownish color is obtained

instead of purple colour , because the absorption occurs at
shorter wavelengths.
Colour change polarization of I2 by the electric field of
solvent dipoles.
TRANSITIONS
 SHIFTS OF BANDS WITH SOLVENTS
1. n→π* transition:
a) This band undergo blue shifts, since ground state with 2
electrons receive greater stabilization than excited state with
only 1 n electron.

2. π →π* transition :
a) As solvent polarity is increased this band undergoes red shift.
b) This is so, since excited state is more polar than the ground
and hence stabilization is greater relative to ground state in
polar solvents.
c) The transition of polar bonds like C=O but not ethylene,
are affected by solvent polarity
Example :
Effect of solvent polarity on spectrum of mesityl oxide:
Influence of solvent on emax of the n* and π excitations of
mesityl oxide
(CH3)2C=CH-C-CH3
2. Purity of solvent:
Purified and certified solvents for spectroscopy should be used
as we are looking for the “smooth” absorbance curve of
solvent.

3. Resolution and interpretation of spectrum

problems:
These are resulted when solvent is used for measurement of
near/below its UV cutoff, i.e the approximate wavelength
below which they cannot be used because of absorption.

4. Dipole moments:
Absorption bands of many substances are relatively sharper
and may also exhibit fine structure when measured in solvents
of low dipole moment.
 EFFECT OF CHROMOPHORE ON UV-
VISIBLE SPECTROSCOPY

The term chromophore was previously used to denote a

functional group, the presence of which gives color to the
compound.
Ex: nitro group is a chromophore because of which compound
attains yellow color.

Chromophore is defined as any group which exhibits

absorption of electromagnetic radiations in the visible or
ultraviolet region.
Ex: ethylene, carbonyl, acids, esters, nitro group.
Chromophores in which the group is having π electrons
undergo π→π* transitions.

Ex: ethylenes, acetylenes

Chromophores having both π electrons and n electrons

undergo two types of transitions.

π→π* and n→π*

Ex: carbonyl, nitryl

TYPES OF CHROMOPHORE
• Conjugated π-bond systems ( resonating system)
• Metal complexes
Conjugated π-bond system chromophores

In the conjugated chromophores, the electrons jump

between energy levels that are extended π orbitals, created by
a series of alternating single and double bonds, often in
aromatic systems.

Egs: azo compounds, pH indicators, lycopene, β-carotene,

and anthocyanins.

Lengthening or extending a conjugated system with more

unsaturated bonds in a molecule will tend to shift absorption
to longer wavelengths
Metal complex chromophores

•The metal complex chromophores arise from the splitting of

d-orbitals by binding of a transition metal to ligands.

•Examples of such chromophores can be seen in chlorophyll,

haemoglobin, hemocyanin, and colourful minerals such as
malachite.
 CLASSIFICATION OF
CHROMOPHORES
• Independent chromophores: When a single chromophore
is sufficient to impart color to the compound. for eg. Azo
group –N=N-,nitroso group, -NO, and o- and p- quinoid
group etc. are independent chromophores.

• Dependent chromophores: When more than one

chromophore is required to produce color in chromogen
for e.g.: acetone having one ketone group is colorless,
whereas diacetyl having two ketonic groups is yellow, and
triketopentane, having three ketonic groups is orange
 Halochromism in chromophores

• Halochromism occurs when a substance changes color as

the pH changes.

• This is a property of pH indicators, whose molecular

structure changes upon certain changes in the surrounding
pH.
Eg: phenolphthalein
Changes in position intensity of absorption:

position of absorption maximum and intensity of absorption

can be modified in different ways by some structural changes
or change of solvent as given below

Bathochromic shift or red shift: It involves the shift of

absorption maximum towards longer wavelength because of
presence of certain groups like –OH, -NH2 which are termed
as auxochromes Or by change of the solvents.
Ex: decrease in polarity of solvent causes a red shift in the n→
π* absorption of carbonyl compounds.
Bathochromic shift is also produced when 2 or more
chromophore are present in conjugation.

Ex: ethylene shows π→π* transition at 170nm where as 1,3-

butadiene shows λmax at 217nm.
Hypsochromic shift or blue shift: It involves the shift of
absorption maximum towards shorter wavelength and may be
caused by removal of conjugation in a system or by change of
solvent.

It is obtained by change in polarity of the solvent.

Ex: In case of aniline absorption maximum takes place at

280mµ because the pair of electrons on nitrogen atom is in
conjugation with the π bond system of the benzene ring.

In acidic solutions, a blue shift is caused and absorption takes

place at short wavelength 200mµ.
Hyperchromic effect: This effect involves an increase in
the intensity of absorption and is brought about by an
auxochrome.

Ex: introduction of methyl group in position 2 of pyridine

increases Ɛmax from 2750-3560.

Hypochromic shift: this effect involves an decrease in the

intensity of absorption and is brought about by an
auxochrome.

Ex: when methyl group is introduced into position 2 of

biphenyl group hypochromic effect occurs.
 Increase in the intensity of
absorption

Peaks shift to shorter Peaks shift to longer

wavelength wavelength

Decrease in the intensity

of absorption
Auxochrome: It is a group which itself does not act as
chromophore but when attached to a chromophore shifts the
absorption maximum towards longer wavelength along with
an increase in intensity of absorption.

Ex: -OH, -NH2, -OR, -NHR, -NR2.

 Auxochromes are of two types :

• Bathochromic groups: the groups which deepens the

colour of the chromogen , are called bathochromic groups .
Deepening of the colour means displacement to longer
wavelength. The bathochromic groups like primary,
secondary or tertiary amino groups, increase the colour

• Hypsochromic groups: those groups which diminish or

lighten the colour of the chromogenic are called
hypsochromic groups. in other words, they cause
displacement to the shorter wavelengths. For e.g., 26

acetylation of –OH or NH2

Effect of conjugation: conjugation of double bonds
lowers the energy required for the transition.

Due to this molecules having conjugated groups exhibit

π→π* absorption bands within the ordinary ultraviolet range.

Ex: buta diene in hexane solution exhibits λmax 217nm. As

the number of double bond increases the absorption moves
to longer wavelength. Hence spectrum of 1,3,5,7 octa
tetraene in hexane exhibits λmax 296nm.

CH2=CH-CH=CH2 (buta diene)

CH2=CH-CH=CH-CH=CH-CH=CH2
(octatetraene)
 Effect of conjugation on absorption spectrum
Increase in conjugation, increase absorbance of light to higher ,
bathochromic shift with hyperchromic effect.
If there are enough double bonds in conjugation absorption
will ultimately move into visible region and the compound
will be colored.

Ex: β carotene naturally occurring yellow pigment having 11

double bonds in conjugation owes its color to absorption in
the visible part of light.
 HOW TO CHOOSE A SOLVENT
• Its transparency

• Its possible effects on the absorbing system

• Generally, polar solvents such as water, alcohols,

esters and ketones tend to obliterate spectral fine
structure arising from vibrational effects.

• It should not itself absorb radiations in the region.

• The position of absorption maxima are influenced by
the nature of the solvent.

• As a rule, the same solvent must be used when

comparing absorption spectra for identification
purposes.

• It should be less polar so that it has minimum

interaction with the solute molecules.