Module 1, Lecture 5
Spectroscopy
Reference Books:
1. Fundamentals of Molecular Spectroscopy, 4th Edition,
by Colin N. Banwell and Elaine M. McCash
2. Introduction to Spectroscopy, 5th Edition, Donald L.
Pavia, Gary M. Lampman, George S. Kriz
3. Organic Spectroscopy By William Kemp 1
Robert Burns Woodward Louis Frederick Fieser
Nobel Prize in Chemistry in 1965
3
Homoannular diene Extended conjugation
(Cisoid or S-cis)
Exo
Heteroannular diene
(Transoid or S-trans)
Acyclic
Exocyclic double bond
Endocyclic double bond 4
Base value (λmax) = 253 nm
Base value (λmax) = 214 nm
Base value (λmax) = 214 nm
5
Empirical rules for dienes
λmax
Parent value:
Homoannular diene 253
Heteroannular diene 214
Increments for:
Each double bond extending conjugation 30
Each Alkyl Residue or ring residue 5
Exocyclic double bond 5
Polar groupings:
-OR 6
-SR 30
-Cl, -Br 5
-NR2 60
-OCOCH3 0
6
------------------------------------------------------------------------------------------
Q1.
Q2.
Q3.
7
Base value : 214
Q4.
Alkyl substitutions (2) : 10
Exocyclic double bond :5
Total : 229
Q5. Base value : 214
4 x alkyl subst. : 20
HO2C
exo DB :5
total : 239
HO2C
Q6.
Base value : 253
O 4 x alkyl subst. : 20
exo DB :5
total : 278
HO2C
8
Q8.
Q9.
9
Q10.
10
Q11.
11
Q12.
12
13
14
15
Application of UV-Visible Spectroscopy
1. Detection of Conjugation: Addition of unsaturation (double or triple
bond) shifts the absorption to longer wave length.
The compound with sufficient conjugation becomes colored
(e.g. Lycopene – gives red colour to tomatoes - 11
conjugated double bonds).
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2. Distinction in Conjugated & Non Conjugated Isomers: It can
differentiate conjugated dienes from non-conjugated dienes; a,b-
unsaturated ketones from b,g-unsaturated ketones.
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3. Detection of Geometrical Isomers:
3.
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19
Winter Semester, End Examination, A
Time: 3 Hours
Time: 3 Hours
CY1001D/CY1001 Chemis
Question. Answer all questions
Time: 3 Hours Answer all questions
1. How can you distinguish the following isomers (A & B) using λmax?
Answer
1. How can you distinguish the following isomers (A all
& B)questions
using λma
1. How can you distinguish the following isomers (A & B) using λm
A B
Compound A: Base value (transoid) = 214 nm
A
Ans. 2-extended conjugation = 2*30 = 60 nm
Compound A:nmBase value (transoid) = 214
lmax : 274 A nm
Compound B: Base value (transoid) = 214 conjugation
2-extended nm = 2*30 = 60 nm
Compound A: Base
1-extended conjugationvalue
= (transoid)
30 nm = 214 nm
l
Ring : 274 nm
max resides 2 (2 x 5) = 10 nm
2-extended
1-ring residueTotal l
= 5 nm = conjugation
284 nm = 2*30 = 60 nm
Compound B: Base value (transoid) = 214 nm
max
lmax : 249 nmlmax : 274 nm
1-extended conjugation = 30 nm
Compound B: Base value (transoid) = 214 nm
2. a) Why impure metals are1-ring residue =to5 corrosion
more susceptible
1-extended
nm
conjugation = than pure metals?
30 nm
Ans: Imagine an impure metallmaxcontaining
: 249 nmdifferent elements of different electrode otentia
1-ring residue = 5 nm
form localised Electrical Cells. As time progresses, the impure metal under the influence
agents, will start to lmaxl:max
Total
corrode.
= 249
249 nmnm (2 Marks)
2. a) Why impure metals are more susceptible to corrosion than pure 20
= (1.67 × 10 kg ) (31.73×10 kg) / (1.67 + 31.73)×10 kg
= 4π2c=2 ṽ=21.5865
µ = 4 ×× 3.14 2
× (3×1010)2 × 39582 × 1.5865 × 10-27 = 8.822 ×102 kgs-2
10-27 kg (1 mark)
ince force
Force constant of HF
constant of HClis,is less than that of HF, bond strength of HCl is also less than that of HF
Question.
k = 4π2c2 ṽ2 µ = 4 × 3.142 × (3×1010)2 × 39582 × 1.5865 × 10-27 = 8.822 ×102 kgs-2 (1 mark)
. ‘With increase in conjugation, λmax for the π→π* transition increases’. Using energy level diagram explain
Since force constant of HCl is less than that of HF, bond strength of HCl is also less than that of HF
this observation with reference to ethylene and 1,3-butadiene. (3 Marks)
Ans: Conjugation in alkenes:
8. ‘With increase The observed
in conjugation, shifts
λmax for the π→π*from conjugation
transition imply
increases’. thatenergy
Using an increase in conjugation
level diagram explain
ecreases
Ans. theobservation
this energy required for electronic
with reference excitation.
to ethylene Extending this effect out to longer conjugated
and 1,3-butadiene. systems
(3 Marks)
he energy gap becomes progressively smaller. (1+1 marks)
Ans: Conjugation in alkenes: The observed shifts from conjugation imply that an increase in conjugation
decreases the energy required for electronic excitation. Extending this effect out to longer conjugated systems
the energy gap becomes progressively smaller. (1+1 marks)
(1 mark)
. a) Write down the electrochemical(1reactions
mark) taking place at anode, cathode and the overall reaction in
9. a) Write down the electrochemical reactions taking place at anode, cathode and the overall reaction in
21
2S [Link].
CY1001D/CY1001 Chemistry
Winter Semester, Test-1 Series, January 2018
CY1001D/CY1001 Chemistry
Answer Key
Question. Answer Key
1.1. When a beam of light (5000 Å) was allowed to pass through a solution in 4 mm
When a beam of light (5000 Å) was allowed to pass through a solution in 4 mm quartz cuvette, the
intensity
intensity of of transmitted
transmitted light
light was was toreduced
reduced 20 % of to 20 %intensity.
its initial of its What
initial
will intensity.
be the
percentage of absorption when the concentration was doubled and the solution was taken in 2 mm
percentage of absorption when the concentration was doubled and the solution
quartz cuvette? (2 marks)
quartz
Answer:
cuvette?
Ans.
A= ecl (from Beer - Lambert’s law)
Answer: (1/2 mark)
l1 = 4 mm, A1 = (100 - 20) % = 80 % = 0.8, c1= x
l2 = 2ecl
A= mm,(from
A2 = ?, Beer
c2 = 2x,- Lambert’s law)
lAs
1 =the
4 mm,
solutionAis1 =same
(100 - 20)
assume that%molar
= 80absorption
% = 0.8, c1= x (e) remains same.
coefficient
lA2 =
1/A2
2 =mm,
c1l1/c2A
l1 2 = ?, c2 = 2x, (1/2 mark)
A2 = c2l2/c1l1 * A1
As
A2 =the
0.8 solution
= 80% is same assume that molar absorption coefficient (e) remains (1 same.
mark)
A1in/Aboth
i.e. 2 = the
c1l1cases
/c2l1the % absorption remains unchanged.
A2 = c2l2/c1l1 * A1
2. The
A2 =absorption
0.8 = 80% maximum of aniline is observed to be at 230 nm. However, the absorption
i.e. in bothshifts
maximum the tocases thein%acidic
203 nm absorption remains
conditions. [Link]. (2 marks)
Answer: When the absorption spectrum of Aniline is recorded in the acidic condition a hypsochromic shift
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2. The absorption
is observed maximum
due to the formation of aniline
of anilinium cation. Inis observed
aniline to ofbe
the lone pair at 230
electron nm. atom
on Nitrogen Howe
A /A = c1l1/c2l1 (1/2 mark)
A=1 ecl2 (from Beer - Lambert’s law) (1/2 mark)
A2 = c2l2/c1l1 * A1
l1 = 4 mm, A1 = (100 - 20) % = 80 % = 0.8, c1= x
A2 = 0.8 = 80% (1 mark)
l2 = 2 mm, A2 = ?, c2 = 2x,
i.e. in both the cases the % absorption remains unchanged.
Question.
As the solution is same assume that molar absorption coefficient (e) remains same.
A1/A2 = c1l1/c2l1 (1/2 mark)
2. A
The absorption maximum of aniline is observed to be at 230 nm. However, the absorption
2 = c2l2/c1l1 * A1
A 2 = 0.8 = 80%
maximum shifts to 203 nm in acidic conditions. Explain. (1 mark)
(2 marks)
i.e. in both the cases the % absorption remains unchanged.
Answer: When the absorption spectrum of Aniline is recorded in the acidic condition a hypsochromic shift
is observed
2. The due tomaximum
absorption the formation
of of anilinium
aniline cation. In aniline
is observed to be the
at lone
230 pair
[Link] However,
electron on the
Nitrogen atom
absorption
can participate in conjugation with the benzene ring, whereas when it is acidified the lone pair is no more
Ans.
maximum shifts to 203 nm in acidic conditions. Explain. (2 marks)
available for conjugation with the ring. (if structure showing conversion of aniline to anilinium cation is
Answer: When 1the
drawn provide absorption spectrum of Aniline is recorded in the acidic condition a hypsochromic shift
mark).
is observed due to the formation of anilinium cation. In aniline the lone pair of electron on Nitrogen atom
3. The partial hydrogenation of the following tetraene gave three products, which are separated by gas
can participate in conjugation with the benzene ring, whereas when it is acidified the lone pair is no more
chromatography. How Woodward-Fieser Rules (λmax) can be used to distinguish the products?
available for conjugation with the ring. (if structure showing conversion of aniline to anilinium cation is
(3 marks)
drawn provide 1 mark).
3. The partial hydrogenation of the following tetraene gave three products, which are separated by gas
Hydrogenation
+ +
chromatography. How Woodward-Fieser Rules (λmax) can be used to distinguish the products?
(3 marks)
Answer: Product 1: (base value: 253 nm) + 15 nm (3-alkyl substituents, 3x5) + 30 nm (1-extended
conjugation) + 5 nm (1-exocyclic double bond). Total = 303 nm. (1 mark)
Hydrogenation 23
Answer: When the absorption spectrum of Aniline is recorded in the acidic condition a hypsochromic shift
can participate in conjugation with the benzene ring, whereas when it is acidified the lone pair is no more
is observed due to the formation of anilinium cation. In aniline the lone pair of electron on Nitrogen atom
available for conjugation with the ring. (if structure showing conversion of aniline to anilinium cation is
can participate in conjugation with the benzene ring, whereas when it is acidified the lone pair is no more
drawn provide 1 mark).
Question.
available for conjugation with the ring. (if structure showing conversion of aniline to anilinium cation is
3. The partial
drawn hydrogenation
provide 1 mark). of the following tetraene gave three products, which are separated by gas
chromatography. How Woodward-Fieser Rules (λ ) can be used to distinguish the products?
3. The partial hydrogenation of the following tetraene max
gave three products, which are separated by gas
chromatography. How Woodward-Fieser Rules (λ ) can be used to distinguish the products? (3 marks)
max
(3 marks)
Hydrogenation
+ +
Hydrogenation
+ +
Answer: Product 1: (base value: 253 nm) + 15 nm (3-alkyl substituents, 3x5) + 30 nm (1-extended
Ans.
conjugation) + 5 nm (1-exocyclic double bond). Total = 303 nm. (1 mark)
Answer: Product 1: (base value: 253 nm) + 15 nm (3-alkyl substituents, 3x5) + 30 nm (1-extended
conjugation) + 5 nm (1-exocyclic double bond). Total = 303 nm. (1 mark)
1
Product 2: (base value: 214 nm) + 15 nm (3-alkyl substituents, 3x5) + 5 nm (1-exocyclic double bond). Total
= 234 nm. 1 (1 mark)
Product 3: (base value: 253 nm) + 15 nm (3-alkyl substituents, 3x5) + 5 nm (1-exocyclic double bond). Total
= 273 nm. (1 mark)
4. The –OH stretching frequencies in the following substituted phenols are observed at 3608 cm-1
(broad) for A, at 3605 cm-1 (broad) and 3643 cm-1 (sharp) for B and at 3643 cm-1 (sharp) for C.
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