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Characterizing Organic
Compounds: Structural Effects
416L
EXPT 3
PAGE 19-20
in Ultra-Violet Spectroscopy
Olivia Cassandra Dela Cruz, John Francis Egenias, Krizzi Eve Garcia*
Department of Chemistry, College of Science
Abstract
Introduction
mainly used in the quantitative determination of various organic and inorganic compounds
in solution. The electronic transitions between molecular orbitals due to the absorption of
radiation in the visible and ultraviolet regions of the electromagnetic spectrum is described
in ultraviolet spectroscopy.3,1
The method of spectroscopy is associated to the interaction of light with matter. The
increase in the energy level of atoms or molecules is due to light being absorbed by
matter. When ultraviolet radiations are absorbed, electrons jump from the ground state
towards a higher energy state which is called the excitation of the electrons. 9 The theory
involved states that the energy from the absorbed ultraviolet radiation is equal to the
energy difference between the higher energy state and the ground state. The wavelength
of the absorbed UV light is dependent by the electronic differences between the orbitals
in the molecule. Depending on the bond, sigma bonds are much stable than pi bonds
which are very likely to come into an excited state. While in conjugated systems, longer
chain of conjugated double bonds absorbs light at a longer wavelength thus affecting the
resulting spectra with the number of observed absorptions.11 The energy changes due to
absorption are relatively large that usually corresponds to a wavelength range of 200 nm
to 800 nm or a wavenumber range of 12000 to 50000 cm-1. The large energy change
solute and solvent molecules that cause collisional broadening of lines in the curve
formed by the spectra are not usually observed in effect with the changes in the energy
levels. While the resulting overlapping bands coalesce to form one or more broad band-
envelopes which are characterized with the position of each maximum λ max and the
complexes, several bands from a number of electronic transitions and their associated
rotational and vibrational fine structures may arise in the complete spectra.10
In obtaining the UV-Vis spectra, the absorption plot must be obtained by the absorbance
determined through the Beer’s law which states the absorbance is directly proportional to
the concentration of the substance and the length of the path of light in the solution and
given by the equation, A = ԑcl.4,5 To measure the UV-Vis spectrum, the sample is
dissolved in a solvent that does not absorb above 200 nm and placed in a quartz cell then
the spectrometer functions by comparing the amount of light transmitted through the
useful in the determination of the structure of molecules that contain conjugated systems
wavelengths greater than 200 nm.2 The measured height of an absorption band above
the baseline of a UV-Vis spectrum is in units of absorbance while its position is given by
the wavelength of the maximum absorbance or λmax, which is measured from the top of
the band.7 The main objective of the experiment is to analyze UV absorptions of organic
UV-Vis spectroscopy.
The purpose of the experiment was to characterize the compounds by their UV-Vis
spectra and analyze the effects of conjugation, type of alkyl groups attached, extent of
annulation and the addition of acids and bases using the method of UV-Vis spectrometry.
The main principles involved are the electronic transitions that arises from the absorption
of visible or ultraviolet (UV) radiation which enables the excitation of electrons thus
moving from a lower energy level to a higher energy level.13 The table below summarizes
acid, phenol added with HCl and NaOH separately and methanolic caffeine also added
λmin : 400 nm
λmin : 362 nm
λmin : 392 nm
Naphthalene λmax : >200 nm; λmin : 344
nm
For the first compound hexane, the obtained spectrum shows that the distinct peak was
recorded at 200 nm for λmax while 400 nm for λmin. The λmax shows the wavelength at
compound hexane, the C-C bonds and C-H bonds have σ-σ* electronic transitions. This
transition requires greater energy at shorter wavelengths.10 With the compound having
no conjugation, λmax was found at 200 nm which is also the same with cyclohexane.
Figure 4. Ultraviolet and visible regions of the spectrum and the types of absorption
Cyclohexane also contained single bonds. The relatively low λmax shows that the spectrum
is shifted on the far UV region also called the vacuum ultraviolet because oxygen in the
air absorbs the more energetic UV photons just below 200 nm.11
For the compound anthracene, the obtained spectrum exhibited a distinct peak at 247 nm
isolated chromophore C=C when conjugated with another C=C, will result to a maximum
absorption band shifting to a longer wavelength along with an increase in its intensity.
Energy changes are lower for substances with a system of conjugated double bonds.8
The fourth compound, naphthalene, the obtained spectra had an absorption maxima of
greater than 200 nm. The added conjugation shifted the spectra towards a longer
wavelength.
For the compound benzoic acid, the resulting spectra showed that the λmax was at 200
nm. When HCl and NaOH was added however, the λmax shifted to a longer wavelength.
The presence of double bonds and an atom conjugated with a lone electron pair causes
less energetically demanding n- π* transition and have a higher λmax. 8 Also, the addition
(a) (b)
(c)
The compound phenol had obtained a spectrum with a λmax of 228 nm which is the same
as benzoic acid and a λmin of 362 nm. Comparing the structure of phenol with benzoic
acid, both compounds have an aromatic ring and double bonds the only difference is the
(a) (b)
(c)
towards a longer wavelength that is both compounds obtained a λmax of 244 nm. This
shift is called the bathochromic effect or red shift wherein the absorption maximum shifts
(a) (b)
(c)
added to 3% HCl and 3% NaOH, the obtained spectrum shifted to a longer wavelength
Scheme 1. Reaction of Caffeine with the addition of HCl results in the protonation of the
Scheme 2. Reaction of Caffeine with the addition of NaOH results in the deprotonation
equilibrium lies to the left based on Le Chatelier’s principle. The protonation of phenol
then results in a blue sift or the shifting to a longer wavelength. On the other hand, the
deprotonation of phenol due to the addition of a base, results in an electron lone pair that
chromophores leads to a bathochromic shift for π-π* transition and hypsochromic shift for
n-π* transitions. The shift is due to resonance effects caused by the interaction of lone
pair electrons in the auxochromes with the π system of the chromophore. 3 While the
annulation or the formation of rings also affects absorption. This is due to the conjugate
system being elongated. The determination of both the shape of the spectra and the
position of the visible maxima are governed by the site of annulation. It causes strong
bathochromic shifts at odd ring positions and hypsochromic shifts at even ring positions.6
The UV absorption of molecules can characterize the compound under study since there
are differences in the promotion of electronic states that is the wavelength at which it
absorbs light can be known. Several factors that affect the UV spectra are level of
conjugation, the presence of alkyl groups, extent of annulation and the changes in pH
due to protonation. For conjugation, the longer chain of conjugated double bonds, the
longer the wavelength at which it absorbs. Likewise, alkyl groups increase the value of
λmax by 5 nm per group. The annulation of aromatic rings also shifts the spectrum to a
Experimental methodology
spectroscopy grade hexane. The solution will be stirred and mixed then transferred into
a quartz cuvette. The UV absorbance will be measured with a range of 200 nm to 400
nm. Then the maximum absorption and wavelength for each band observed will be noted.
The sample pair assigned to the group will be compared and contrasted.
In obtaining the spectra for the aromatic systems, naphthalene and anthracene, the same
procedure will be adapted. With the maximum absorption and wavelength noted, the
obtained spectra for the aromatic system will be compared and contrasted with the
A milligram of the assigned sample aromatic compound, phenol, will be weighed and
the first and second part, the solution will be stirred and mixed then transferred on a quartz
cuvette. The UV absorbance will be measured ranging from 200 to 400 nm with the use
of a UV-Vis spectrophotometer. Also, the maximum absorption and wavelength for each
band observed will be noted. After obtaining the first spectra, the sample will be returned
to the original mixing vessel and 3 drops of 5% HCl will be added then stirred and
transferred into a quartz cuvette. The UV absorbance will be measured again with the
same range then the obtained spectra will be compared and contrasted with the first
spectra obtained.
References
2. Ault, A. Techniques and experiments for organic chemistry, 4th ed.; University Science
4. Hart, D. J.; Hart, H.; Hadad, C. M.; Craine, L. E. Organic chemistry: a short course,
5. Hesse, M.; Meier, H.; Zeeh, B.; Dunmur, R.; Murray, M. Spectroscopic methods in
to the laboratory course; Pearson Prentice Hall: Upper Saddle River, 2010.
11. Wade, L. G.; Simek, J. W. Organic chemistry, 9th ed.; Pearson Education Limited: