C3307 – CC3340

Homework II

Ultraviolet-visible Spectrometry (UV-Visible)

I. Identify the possible electronic transitions for:

a) CH4; b) CH3Cl; C) H2C=O?
In
a) CH4: Transitions   *
b) CH3-Cl: Transitions   * and n  * (no  or *)
c) H2C=O : Transitions   *, n  *,   * and n  *.

II. UV spectra for Acetone shows two bands at λmax = 280 nm, max = 15 and λmax = 190 nm,
max = 1000.
a) Identify the electronic transition for each band.
b) Which one represents the higher intensity?
The most intense transition is the one with the highest value of max, so the band having
max = 1000 is more intense than the band having max = 15.
The band at 280 nm is in the near UV and has a very low value of max (max = 15),
therefore, it is attributed to a transition of type n   *.
PS: n  σ * in the case of oxygen is in the far UV (<200 nm).
The transition at 190 nm has a εmax = 1000. Such a value of εmax cannot be attributable to
a transition n → σ *. It is therefore an isolated π → π * transition, isolated π → π *
actually absorbs at values of λmax from 170-195 nm.

III. The UV spectra of a 2 × 10-4 mol.L-1 pent-3-en-2-one solution shows an absorption π → π*

at 224 nm with A = 1.95, and another n → π* band at 314 nm with A = 0.008.
Calculate the molar absorptivities for these bands. Conclude.
A
ε=
A = lC  l.C
1 , 95
ε max = −4
=9 ,75 . 103 = 9750 mol−1 L. cm−1 .
For the transition   * : 1. 2. 10
 0 , 008
ε max = −4
=40 mol−1 L. cm−1
For the transition n  * : 1. 2. 10
max for   * is almost equal to 104 mol-1.L.cm-1  allowed transition.
max of n  * << 103  forbidden transition.
max of n  * << max of   *
The transition n  * is less probable to occur than the transition   *.

IV. Ethanol, methanol and cyclohexane are commonly used solvent in UV-Vis spectroscopy
because they do not absorb radiations with a wavelength higher than 200 nm. Explain the
reason for this.
These molecules have no  bond. They only contain single bonds. Hence we can exclude
for these molecules any transition of type n   * (which is of low energy and which
generally takes place in the near ultraviolet). The    * transitions are also excluded.
For these three molecules, we can observe transitions of type    * which require a lot
of energy and therefore take place in the far ultraviolet (10-200 nm). For ethanol and
methanol, the transitions n   * take place in the far ultraviolet. These solvents are
therefore transparent at wavelengths greater than 200 nm and can be used as solvents in
this field, one of the conditions for choosing the solvent being its transparency in the
spectral region studied.

V. Classify the following compounds starting with the one showing the smallest value for
UV-Vis λmax (without calculating λmax).
(a) cyclohepta-1,3,5-triene; (b) hexa-1,5-diene; (c) cyclohexa-1,3-diene;

(d) e) polyacetylene ; (f)

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The more extensive the conjugation, the higher the value of the wavelength at maximum
absorption max in UV-visible. Hence the classification, in ascending order of wavelength
max in UV-visible, according to:
b < c < a < f < d < e.
Conclusion: ultraviolet and visible spectroscopy provides a means of assessing the extent
of conjugation within a molecule.

VI. Explain why λmax (nm) varies in the following compounds CH3X : 
X = Cl (173), Br (204) and I (258).
The transition involved in this case must be n   *. Going from Cl to Br then to I:
(a) We find the non-binding electrons n in the main high energy levels (the principal
quantum numbers being respectively 3, 4 and 5) (3s23p5, 4s24p5, 5s25p5).
(b) The electrons become farther from the attractive force of the nucleus.
(c) The electrons can be excited more easily.
The absorption therefore occurs at increasingly high max values.

VII. Identify the two geometrical isomers for stilbene, C6H5CH=CHC6H5, using the values
λmax: 293 nm and 278 nm.
The shortest wavelength is associated with the highest energy cis isomer. Steric
compression prevents complete coplanarity (coplanarity) of the phenyl groups in the cis
product and the conjugation effect is attenuated.

VIII. Three flasks each containing one of the following isomers of C6H10 had lost their labels:
hexa-1,4-diene, hexa-1,3-diene cis et hexa-1,3-diene trans.
Studying the contents of the three flasks by UV-Vis spectroscopy give the following results:
λmax 176, 211 and 216 nm. Assign each λmax to the suitable compound. Justify.

hexa-1,4-diene : H2C=HC-H2C-HC=CH-CH3
hexa-1,3-diene cis and hexa-1,3-diene trans : H2C=HC-HC=CH-CH2-CH3
Hexa-1,4-diene: No conjugated double bonds so absorbs at 176 nm (similar to ethene
which absorbs at 170 nm).

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Cis hexa-1,3-diene absorbs at 211 nm and trans hexa-1,3-diene absorbs at 216 nm. The
cis isomer absorbs at shorter wavelengths (higher energies) than the trans isomer. The
conjugation being attenuated in the cis compound, its wavelength at the maximum
absorption max is then lower.

IX. A compound (A) having the formula C11H16O can be hydrogenated in the presence of
palladium to form the compound (B), with the formula C11H18O and showing the following
structure:

The ultraviolet spectra of the compound (A) shows a high intensity absorption band at
λmax = 225 nm that disappears in the spectre of the compound (B). Deduce the structure of the
compound (A)?

In the statement, it is specified that it is about a strong band therefore it is about a

transition    * and not n   *. Compound (B) is obtained after hydrogenation of
compound A, therefore in compound (A), there was a double bond which no longer
exists in compound (B). This double bond must be conjugated with the double bond C =
O because its disappearance affects the value of max of the double bond C = O. (If it
were not conjugated with the double bond C = O, it would not have affected the value of
max of the latter). In addition, if it were not conjugated with the double bond C = O, the
value of max of the latter would not be 225 nm (near UV region) but in the far ultraviolet
(max of transitions    * isolated double bonds are found in the far ultraviolet, max of
transitions    * conjugated double bonds are found in near ultraviolet or in visible.
max of transitions    * of C = O of a saturated ketone is found around 190 nm).

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Three structures are therefore possible for compound (A):
A1 : A2 : A3 :

Let us calculate the value of max of the transition    * of the group C = O in each of
these compounds and deduce the good structure of the compound (A). Table 5.7
For the compound A1 :
Parent system : acyclic keton : 215 nm
Ring residue on  : + 10 nm
Exocyclic bond : + 5 nm
 maxcalc = 230 nm.

For the compound A2 :

Parent system : acyclic keton : 215 nm
Alkyl group on  : + 10 nm
2 ring residues on  : + 2  12 nm
Exocyclic double bond : + 5 nm
 maxcalc = 254 nm.

For the compound A3 :

Parent system : acyclic keton : 215 nm
Ring residue on  : + 12 nm
 maxcalc = 227 nm.
Or maxobs = 225 nm is the closest to maxcalc = 227 nm, so the compound A is A3.

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XI. The following compounds show experimentally in the ultra-violet spectroscopy a
principal absorption band with a localization in perfect harmony with the theoretical
previsions calculated according to Woodward, Fieser and Scott’s rules
A) What are the experimental localizations in the solvent ethanol ?
B) Predict these localizations for the products d, e, f, g et h in water and cyclohexane
solvents.
a)

Parent system conjugated diene : 217 nm

Ring residue on a, b and c : + 3  5 nm
Exocyclic double bond : + 5 nm
 maxcalc = 237 nm.

b)

Parent system conjugated diene : 214 nm

Ring Residue a, b, c and d: + 4  5 
2 exocyclic double bonds : + 2  5 
 maxcalc = 244 nm.

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c)

Parent system conjugated diene : 217 nm (the one within the ring)
Double bond extending the conjugation : + 30 nm
Diene system within the ring : + 36 nm
3 exocyclic double bonds : + 3  5 nm
Ring residues, a, b, c, d and e : + 5  5 nm
 maxcalc = 323 nm.

d)

Parent system conjugated diene : 217 nm (the one within the ring)
Double bond extending the conjugation : + 30 nm
Diene system within the ring : + 36 nm
3 exocyclic double bonds : + 3  5 nm
Ring residues, a, b, c, d and e : + 5  5 nm
 maxcalc = 323 nm.

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e)

Six ring keton parent system : 215 nm

OH on  : + 35 nm
Ring residue and alkyl group on  : + 2  12 nm
 maxcalc = 274 nm.
f)

Five ring keton parent system : 215 nm

Alkyl group on  : + 10 nm
2 Ring residues and on  : + 2  12 nm
Exocyclic double bond : + 5 nm
 maxcalc = 241 nm.

g)

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Six ring keton parent system : 215 nm
Double bond extending the conjugation : + 30 nm
Exocyclic double bond : + 5 nm
Ring residue on  : + 12 nm
Ring residue on  : +18 nm
 maxcalc = 280 nm.
h)

In this case we have 2 choices for the parent system: we always chose the most substituted
structure
Six ring keton parent system: 215 nm
Exocyclic double bond: + 5 nm
Ring residue on  : + 2  12 nm
 maxcalc = 244 nm.

i)

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Acyclic keton parent system: 215 nm
Exocyclic double bond: + 5 nm
Ring Residue on  : + 10 nm
(Cl and OCH3) on  : + 12 and + 30 nm
 maxcalc = 272 nm.

j)

Six ring keton parent system: 215 nm

Double bond extending the conjugation: + 30 nm
Diene system within a ring: + 39 nm
Exocyclic double bond: + 5 nm
Ring residue on  : + 10 nm
Ring residue on  : +18 nm
 maxcalc = 317 nm.

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k)

Parent system : -CO-R : 246 nm

Substituent : OH on meta : + 7 nm
 maxcalc = 253 nm.

l)

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Parent system: -CO-R : 246 nm
Substituent : Alkyl group (éthyle) on ortho : + 3 nm
Ring residue on ortho : + 3 nm
Br on meta : + 2 nm
 maxcalc = 254 nm.

m)

Parent system : -CHO : 250 nm

Substituent : 2 OH on ortho : + 2  7 nm
Alkyl group on meta (méthyle): + 3 nm
Group OR (méthoxy) on para : + 25 nm
 maxcalc = 292 nm.

n)

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B) The product d is a conjugated polyene. It only has the chromophore C = C. The bond C =
C is apolar and consequently it is little influenced by the polarity of the solvent. Therefore, the
maximum absorption wavelength max of the transition    * of this chromophore remains
the same in the solvents ethanol, water and cyclohexane
The products e, f, g, h and i are enones. However for these compounds, the transition    *
undergoes a bathochromic displacement when the polarity of the solvent increases and
hypsochrome when the polarity of the solvent decreases. Water is more polar than ethanol, so
in the water solvent, the values of max for these compounds become

e : maxcalc = 274 + 8 = 282 nm 

f : maxcalc = 241 + 8 = 249 nm
g : maxcalc = 280 + 8 = 288 nm 
h : maxcalc = 244 + 8 = 252 nm
i : maxcalc = 272 + 8 = 280 nm.
Cyclohexane is less polar than the ethanol solvent, therefore the max values of these
compounds become

e : maxcalc = 274 - 11 = 263 nm

f : maxcalc = 241 - 11 = 230 nm
g : maxcalc = 280 - 11 = 269 nm
h : maxcalc = 244 - 11 = 233 nm
i : maxcalc = 272 - 11 = 261 nm.

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