UV – VISIBLE

SPECTROSCOPY
CHOICE OF SOLVENT , SOLVENT EFFECTS
AND APPLICATIONS OF UV-VISIBLE
SPECTROSCOPY

PRESENTED BY PRESENTED TO
VARSHITHA S Prof. BIDYA BHUSHAN
DEPT OF PHARMACEUTICS
1ST SEM M PHARM
CONTENTS
• CHOICE OF SOLVENTS

• SOLVENT EFFECTS

• APPLICATIONS

• REFERENCE
 CHOICE OF SOLVENTS

A solvent is a liquid that dissolves another solid, liquid, or gaseous solute, resulting in a solution at a
specified temperature.
• The solvent exerts a profound influence on the quality and shape of spectrum.

Solvents can be broadly classified into two categories:

•Polar
•Non-Polar
★ A drug may show varied spectrum at a particular wavelength in one particular condition but shall
absorb partially at the same wavelength in another condition.
★ 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
CHOICE OF SOLVENT
•The absorption bands in the ultraviolet spectrum are very broad as compared with the NMR spectrum.
•Ultraviolet spectra of compounds are usually determined either in the vapour phase or in very dilute solution.
•Solvent must be transparent within the wavelength range being examined.
A solvent for UV spectroscopy should meet the following requirements:
☑ It should not itself absorb radiation in the region under investigation.
☑ It should be less polar to minimize interaction with the solute molecule.
☑ Spectroscopic (Analytical) grade solvents should be used.
☑ The most commonly used solvent is 95% ethanol, because:
•It is cheap.
•Good dissolving power.
•Does not absorb radiation above 210 nm.
☑ Some other solvents that are transparent above 210 nm:
•n-hexane, cyclohexane, methanol, water, and ether
•Hexane and other hydrocarbons are sometimes preferred to polar solvents because they have minimal interaction
with solute molecules.
•Benzene, chloroform, and carbon tetrachloride cannot be used because they absorb in the range of about 240 - 280
nm.
•Generally, polar solvents such as water, alcohol, esters, and ketones tend to destroy the fine structure due to
vibrational effects.

Solvents for Electronic Spectroscopy

 SOLVENT EFFECTS
Polarity

Polarity plays an important role in the position and intensity of absorption maximum
of a particular chromophore.

a) In the case of non-polar solvents, e.g., iodine solution (purple color), the
absorption maxima occur at almost the same wavelength as in iodine vapor (5180
Å).

b) In the case of polar solvents, a brownish color is obtained instead of purple color,
because the absorption occurs at shorter wavelengths.

•Color change occurs due to the polarization of I₂ by the electric field of solvent
dipoles.
EFFECT OF SOLVENT POLARITY ON N→Π* AND Π →Π* TRANSITIONS
 n*
• If the chromophore involved in the transition is more polar in its ground state than
in its excited state, then the ground state is more stabilized than the excited state by
a more polar solvent due to solvation. Chromophores with n→* or n* transitions
exhibit such behavior.

• On excitation, the charge distribution in such systems changes markedly and

therefore, the solvent molecules would not have position and orientation to interact
with the excited state charge distribution.

• Thus, the ground state of such solute molecules is more stabilized than the excited
state.
• This widens the energy gap between the ground and excited states with increasing
polarity of the solvents.

• Therefore, more energy is required for the n→*kind of electronic transition with
increasing solvent polarity. This results in the shift of spectral peak positions
towards shorter wavelength. (Hypsochromic shift).

• In the case of n* transition, the absorption band is shifted to shorter wavelength (the
nbands undergo blue shifts) by increasing the polarity of the solvent, because ground
state with two electrons receives greater stabilization than the excited state with only
one n-electron.

• For example,
In polar solvent like water, acetone absorbs comparatively at lesser wavelength
(λmax 264.5) than the non-polar hexane solvent 279 nm).
 *
• If the excited state of the chromophore is more polar with respect to the ground state,
then the excited state will be more solvated and more stabilized by a more polar
solvent. This kind of property is observed in the case chromophores with π→π*
transitions.

• The electron density is equally distributed in the ground state and the C nuclei are
shielded whereas in the * excited state the C nuclei become electron deficient due to
the electron promotion.

• This favors stronger interaction of the excited state molecule with more polar or
hydrogen bonding solvents and thereby stabilizing the excited state more than the
ground state.
• This decreases the energy gap between the excited and the ground states with
increasing solvent polarity which results in shift of absorption peak positions towards
longer wavelengths. (Bathochromic shift).

• The transitions of polar bonds like carbonyls (not ethylenes) are affected by the
polarity of solvent. The * bands undergo bathochromic shift or red shift as the solvent
polarity is increased but n * bands undergo hypsochromic shift or blue shift as the
solvent polarity is increased.

• The organic molecules such as butadiene, mesityl oxide etc. with conjugated in
systems show K-bands because of * transitions.
Ex: Effect of solvent polarity on the spectrum of mesityl oxide.

Solvent * (𝛆) n* (

n-Hexane 230 (12600) 327 (98)

Ether 230 (12600) 326 (96)

Ethanol 237 (12600) 315 (78)

Water 245 (10000) 305 (60)

Red shifts Blue shift
 THE FOLLOWING POINTS MAY AFFECT SOLVENT
POLARITY ON VARIOUS TYPES OF BANDS:
K BAND

Transition:*

Examples:
1) dienes, polyenes, enones etc conjugated system containing compounds.
2) Aromatic compounds substituted by chromophores.

Intensity: 104

Solvent effect:
• 'enes' and 'enones' are affected differently by changing the polarity of the solvent.
• Enones show red shift with increasing the polarity of the solvent.
 R BAND

Transition: n*
Cause: Unsaturated compounds containing heteroatoms.
Intensity: less (below 100)
• Also called forbidden bands.
Solvent effect: With increase in polarity of the solvent shifts to shorter
wavelength. (blue shift).

B BAND
Transition: π→*
Cause: double bond containing aromatic or hetero-aromatic molecules.
Intensity: more than R-band.
Solvent effect: hyperchromic shift in heterocyclic aromatic compounds.
Examples: benzene, styrene phenol etc.
E BAND
TRANSITION : π→*
SOLVENT EFFECT : HYPSOCHROMIC SHIFT (BLUE SHIFT )
EXAMPLES : ETHYLENE
 E BAND

TRANSITION : π→*
SOLVENT EFFECT : HYPSOCHROMIC SHIFT (BLUE SHIFT )
EXAMPLES : ETHYLENE
 IDENTIFY
UNKNOWN
COMPOUND

QUANTITATI
VE
ANALYSIS FOOD
INDUSTRY

APPLICATION
S

QUALITATI
VE PURITY
ANALYSIS STUDIES

STRUCTURAL
ELUCIDATION
 APPLICATIONS

• Detection of functional groups: To detect the presence or absence of chromophore.

• Extent of conjugation: The extent of conjugation in polynes R-(CH=CH)n-R can be

estimated.

• Qualitative analysis / Identification of an unknown compound: An unknown

compound can be identified by comparing its spectrum with the known spectra.

• UV/VISIBLE spectroscopy is used as a tool to identify if the analyte is pure and did not
undergo decomposition.

• In food & beverage industry: To monitor and improve product quality and consistency.
• Distinction in conjugated & non-conjugated compounds: It also
distinguishes between a conjugated & a non-conjugated compound.

• Structure elucidation of organic compounds.

• Determination of pKa value of indicators: pKa = pH - [log

(ionized/unionized)].

• Quantitative analysis:
*Using εmax values (E1%1cm)
*Raw material
*Direct comparison method 24
*Calibration curve method
 REFERENC
E

1. Instrumental methods of Chemical Analysis Dr. B. K. Sharma

https://www.slideshare.net/slideshow/solvents-and-
2.
solvent-effect-in-uv-vis-spectroscopy-by-dr-umesh-
kumar-sharma-and-susan-jacob/150038106