Block 2 Spectros

CHEM110/Block 2/Spectroscopy/2020 1
CHEM110 2020
CHEMISTRY OF THE LIVING WORLD
BLOCK 2: SPECTROSCOPY
AND STRUCTURE DETERMINATION
Lecturer: Dr Melissa Cadelis

email: m.cadelis@auckland.ac.nz
This handout should be brought to all lectures.

Please fill in the section below. Should you misplace this handout it will assist us in returning it
to you. Anyone finding this handout should take it to Chemistry Reception, Level 6 of Building
302 (Science Centre).
Name:
Laboratory Day and Time: Bench Number:
At the end of this block you should be able to:

• Describe the main characteristics of MS, UV-VIS, IR and NMR spectroscopy.
• Relate spectroscopic techniques back to principles of electromagnetic radiation.
• Describe the strengths and limitations of MS, UV-VIS, IR and NMR spectroscopy
• Relate spectroscopic information to structural features in an organic molecule.
• Determine the structure of organic compounds given appropriate spectral information.
• Show how UV-Vis spectroscopy can be used for quantitative measurement.
© School of Chemical Sciences The University of Auckland

Pre-Lecture Reading Lecture 1

INTRODUCTION
Spectroscopic techniques allow most functional groups to be detected rapidly and often a full
determination of the structure of compounds. Most spectroscopic methods are non destructive
with respect to the sample (the exception being MS, see below).
This course introduces the following spectroscopic techniques:

1. Mass spectrometry (MS)
• Examines ions derived from organic molecules and allows us to determine
the molar mass of a molecule.
2. Infrared spectroscopy (IR)
• Determines the presence or absence of particular functional groups in molecules
including OH, NH, C=O, C=C and C-O groups.
3. Ultraviolet-visible spectroscopy (UV-VIS)
• Determines the presence of pi-bond electrons in a molecule as well as the presence
of any conjugation in the structure of the compound.
4. Nuclear magnetic resonance spectroscopy (NMR)
• Provides information about the carbon and hydrogen framework of a molecule.
Techniques IR, UV-Vis, and NMR are forms of spectroscopy collectively known as molecular
spectroscopy. These techniques depend on the interaction of molecules with radiation of
specific energy; spectroscopy being the study of the interaction of electromagnetic radiation
with matter.
Note that mass spectrometry (MS) does NOT study the interaction of a molecule with radiation
– it is a completely different technique to the other three.
The fundamental importance of molecular spectroscopy is that absorption of radiation of

particular frequencies is found to be characteristic of specific structural units (functional
groups) in a molecule. Therefore if we measure the absorption spectrum of a molecule (using
either IR, UV-Vis, or NMR techniques) we can use this spectrum to determine the presence or
absence of functional groups in a molecule. Combining all the MS and molecular spectroscopy
information can help us distinguish between possible molecule structures or they can even
help us determine the complete structure of a molecule.
The electromagnetic spectrum extends from high energy cosmic rays to low energy radio
waves.

The fundamental equations of electromagnetic radiation are:
(1) E = hν (2) c = νλ (3) E = hc / λ (4) ν = 1/ λ

Where E = energy of the radiation, c = velocity of light, and h = Planck’s constant
and ν = frequency, and λ = wavelength of the radiation, and ν = wavenumbers.

Since ν and λ are related by a constant (c) (equation 2), the energy of the radiation (E) can
be described by either the frequency (ν) (equation 1) or the wavelength (λ) (equation 3).
Relationship 4 above is only important when we discuss IR spectroscopy.
Of particular note is that Energy is directly proportional to frequency (equation 1), while
Energy is inversely proportional to wavelength (equation 3). Therefore smaller energy relates
to a smaller frequency of the electromagnetic radiation, while that same smaller energy relates
to a larger (longer) wavelength of radiation. These relationships are important to remember
when we look at IR, UV-VIS and NMR spectroscopic techniques.
The fundamental basis of molecular spectroscopy is that when the energy of the electromagnetic
radiation put onto a sample exactly corresponds to the energy difference between two
molecular energy levels, then the molecule can absorb the energy. The molecule is said to go
from the ‘ground state’ to an ‘excited state’.
Consider:
E2 E2
E molecular energy levels .
E1 E1
This transition will occur when the energy of the electromagnetic radiation = E2 – E1 (ΔE)
Therefore, we would observe an energy absorption at ΔE = hν
Therefore only one frequency of radiation will be applicable to a particular transition. This
means that the absorptions of energy that are detected using molecular spectroscopy are
entirely predictable and can tell us specific things about the structure of the molecule.
The spectrum of a compound is a ‘graph’ of the fraction of radiation absorbed or transmitted

by the sample versus the wavelength, frequency or wavenumber of the light impinging on the
sample.
Practice Question Two compounds, 1 and 2, have molecular energy levels as shown. ΔE for
compound 1 is smaller than the ΔE value of compound 2. Which compound has an energy
transition corresponding to a shorter (smaller) wavelength of radiation? Justify your answer.
compound 1 compound 2
E2
E2
E E
E1 E1

1. MASS SPECTROMETRY
Mass spectrometry is routinely used in the analysis of the composition of organic compounds.
Mass spectrometry allows the determination of the mass of individual ions derived from
compounds in the gas phase.
The most common method for the generation of ions from organic compounds is electron
impact, that is the molecule is bombarded with a high energy electron beam.
The ionised molecule (molecular ion) results from the expulsion of (usually) one electron and
is therefore a radical cation.
A plot of the relative ion abundance versus m/z (m = mass of the ion; z = charge of ion) is the
mass spectrum.
The molecular ion (parent ion, M+•)
must be the ion of highest m/z (z = 1).
The major limitation of mass spectrometry is that by consideration of the mass of M+• alone, it
is not possible to distinguish between compounds with the same molecular formula (isomers).
It’s also worth noting that it is also not possible to distinguish between different molecular
formulae that have the same integer mass:
For example: C11H24N2O (m/z 200) and C10H20N2O2 (m/z 200)
Practice Question:
CH3CH2CH2OCH3 CH3CH2CH2OH (CH3)2CHOCH3

A B C

2. IR SPECTROSCOPY
Units used: ν ( cm−1 ), where ν = 1 / λ
that is increasing the amplitude
IR radiation absorption corresponds to vibrational excitation;
of the vibration. Absorption of IR radiation occurs when the radiation frequency exactly
matches the frequency of bond vibration.
% Transmittance
Wavenumber (cm-1)
Such bond vibrations are either stretching:
or bending:
(bond angle change)
Note that in IR spectra the relative masses of atoms involved and bond strengths determines
the position of an IR absorption.
IR spectra are quite complicated, so we don’t try to identify all the absorption bands in the
spectrum. We look at specific ‘zones’ to determine whether a particular functional group is
present or absent from the molecule.
TABLE 1
IMPORTANT INFRARED ABSORPTION REGIONS
(STRETCHING FREQUENCIES)
Bond Present ν (cm 1)−
O−H (alcohol, phenol) 3700 – 3200

(carboxylic acid) 3600 – 2500 (broad)
N−H 3500 – 3100
C−H 3100 – 2800
C=O 1850 – 1600
C=C (aliphatic) 1680 – 1600
(aromatic) 1620 – 1550
C−O 1250 – 1050 (less definitive)

2.1 THE UTILITY OF IR SPECTROSCOPY
i) For rapid identification of functional groups.
ii) As a ‘fingerprint’, as no two compounds have identical spectra.
O
2.2 IR PROBLEMS CH3CCH3,
CH3CH2OCH2CH3
i) The compounds shown at the right give rise to IR spectra 1 – 3.
NH2
Decide which of the three compounds gives rise to each spectrum.
and
ii) For the IR spectra given below, decide which of the compounds listed is most likely
to have given rise to the spectrum.
OH CO2CH3
A:
OCH3 CH2CH3

B: CH3CO2H
CH3CH2OCH3
CH3CH2CH2OH
CH3CO2CH3


3 UV-VIS SPECTROSCOPY
Khan academy video: https://www.khanacademy.org/science/organic-chemistry/
spectroscopy-jay/uv-vis-spectroscopy/v/uv-vis-spectroscopy. Link available on Canvas
(Block 2).
Note: the video mentions terms HOMO (highest occupied molecular orbital) and LUMO (lowest
unoccupied molecular orbital). These terms are not examinable in this section of the course,
but the underlying principles of electron excitation etc. are.
Ultraviolet-visible radiation is of appropriate energy to raise electrons in some molecules

(generally those with π electrons) from lower energy bonding (or non-bonding) molecular
orbitals to higher energy anti-bonding molecular orbitals.
Thus using our energy level diagram, UV-VIS radiation is the correct energy to cause the
transition of an electron from a lower energy (ground state) to a higher energy (excited state)
level.
E2 E2
E molecular energy levels .
E1 E1
This transition will occur when the energy of the electromagnetic radiation = E2 – E1 (ΔE)
When discussing UV-VIS spectroscopy, an important structural feature, conjugation, of some

organic molecules should be considered. ‘Conjugation’ means ‘to link together’ and in a
chemistry context it refers to π-electron systems (i.e. double bonds) that are ‘linked together’.
It is important to be able to recognize π-electron systems that are conjugated, as conjugated
systems exhibit different UV-VIS absorbance when compared to non-conjugated systems. The
motif to recognize is that double bonds are conjugated when there is only ONE single bond
between the double bonds e.g. double-single-double.
Practice Question: . State whether the molecule contains a conjugated π-system or not.
a) b)
O
c) d)

The UV-Vis Spectrum
λ = ~200 – 400 nm (UV); 400 – 800 nm (VIS) E = ~150 – 600 kJ mol−1
Ultraviolet-visible radiation is of appropriate energy to raise electrons in some molecules
(generally those with π electrons) from lower energy bonding (or non-bonding) molecular
orbitals to higher energy anti-bonding molecular orbitals.
UV-VIS spectrum is a plot of absorbance (Y-axis)

versus wavelength of radiation [X-axis, units of
nanometres (nm)]. The wavelength at which
maximum absorbance is observed is known as
the λmax.
Compounds containing only σ-bonds are generally transparent to UV-VIS light.
i) C=C
ii) C=O
Note: ΔE n → π* < ΔE π → π* and so the absorption for n → π* is at longer λ than π → π*.

3.1 Conjugated Systems
In conjugated systems (that is those with alternating single and double bonds) ΔE for electron
excitement is smaller.
Examples: CH2=CHCH2CH2CH=CH2
CH3CH=CHCH=CHCH3
CH=CH2
CH3 CH3 CH3
CH2OH
CH3
CH3
Any molecule containing conjugated double bonds will show an absorption at >200 nm. The
greater the number of double bonds in conjugation:
3.2 UV-Vis and Beer’s (Beer-Lambert’s) Law

The intensity of an absorption is defined by
Absorbance, A = log10(I0/I)
(where Io is incident light, I is transmitted light).
For a particular compound at a specified λ:
and the more “effective” a molecule is at absorbing light at that wavelength, the greater is the
absorbance.
Beer’s Law:

Examples:
O
CH3CCH3
(CH3)2C=CHCH2CH3
O2N
(CH3)2C=NNH NO2
For strongly-absorbing solutes, ε is usually in the range 105- 106 L mol−1 cm−1 so very low
concentrations (about 10−5 - 10−6 mol L−1) must be used.
3.2.1 Utility of Beer’s Law

To determine the concentration in solution of a UV-VIS absorber of known structure by:
i) Finding the absorbance at λmax and substituting into Beer’s Law if the molar absorptivity
at λmax is known.
Example: For a solution of camphor in hexane in a 1 cm path length cell, the absorbance at 295
nm was found to be 0.80. Given that the molar absorptivity at 295 nm is 14 L mol−1 cm−1, what
is the concentration of the camphor?
ii) Making a calibration plot for solutions of known concentration at a specific wavelength.
Then at the same wavelength determine the absorbance x

for the solution of unknown concentration, and read off the A x
concentration from the calibration plot. x
x
x
concentration

4 MS, UV-VIS and IR and structure determination
Consider the following:

i) A compound is known to have the molecular formula C3H6.
DBEs = ½(2n4 + n3 – n1 + 2) = ½(6 + 0 – 6 + 2) = 1
∴ one π bond or ring → Compound must be an alkene or a cycloalkane.
OR alkene:
UV: π-π* absorption ~ 170 nm
cycloalkane alkene
IR: C=C absorption 1680-1600 cm-1
The structure of the compound can be determined using either UV-VIS or IR spectroscopy.
ii) A compound with a molecular formula of C5H10 has DBE = 1.
cycloalkane alkene
alkenes:
UV: π-π* absorption ~ 170 nm
OR
IR: C=C absorption 1680-1600 cm-1
Using either UV-VIS or IR spectroscopy it can be determined whether the compound is

a cycloalkane or an alkene. However, it is not possible to determine the specific alkene or
cycloalkane using MS, UV-VIS and IR.
iii) A compound has the molecular formula C3H8O.

alcohol ether
OH OR
OH O
IR: O-H absorption 3700-3200 cm-1 IR: C-O absorption 1250-1050 cm-1
C-O absorption 1250-1050 cm-1 (no O-H absorption)
IR allows one to distinguish between alcohol and ether possibilities. However, if this shows
the compound is an alcohol these three spectroscopic methods do not allow determination of
which particular alcohol the compound is.
Conclusion:

REVISION EXERCISES FOR PART 1 OF BLOCK 2
1. Which of the following would be expected to show an absorption above 200 nm in the
UV VIS region of the electromagnetic spectrum?
i) hexa-1,5-diene ii) pent-1-en-3-ol iii) hexan-3-one
iv) cyclohex-2-enone v) hexa-2,4-diene vi) cyclopentanone
2. A 5.0 × 10−5 mol L−1 solution of 1,2-diphenylethene in a 1 cm path length cell has an
absorbance of 1.60 at 280 nm. Calculate the molar absorptivity.
3. If a solution of a pure compound of concentration 1.4 × 10−3 mol L−1 has an absorbance
of 0.82 at 245 nm, what is the concentration of a solution of this compound if it has an
absorbance of 0.34 at the same wavelength?
4. For the IR spectra given below, decide which of the compounds listed is most likely to
have given rise to the spectrum.
A: CH3CO2H
CH3CO2CH3
CH3CH2OH
(CH3CO)2O
B: CH3CH2OCH3
(CH3)3N
CH3(CH2)5NH2
CH3(CH2)5CH3
C: OH CO2H
O
OCH3 CCH3
5. Name the functional group present in each of the following compounds. Indicate the
position and nature of the absorption that would allow each pair to be differentiated
using IR spectroscopy.
i) CH3CH2CH2OH and CH3CH2CHO iv) CH3CH2CH2NH2 and (CH3)3N
ii) CH3CH2OH and CH3CH2CH2CH3 v) CHO CO2H
iii) CH3CH2CO2H and CH3CO2CH3
and
6. For each pair of compounds given in Q5, state whether the mass of the molecular ion in
the mass spectrum would allow one to differentiate between the pair of compounds.
7. A compound is known to be mono-functional; that is it contains one functional group.

It has the empirical formula C2H4O and the molecular ion in its mass spectrum is at mass
88. Indicate to what extent its structure could be determined on the basis of MS, UV-VIS
and IR spectra.


Khan video: https://www.khanacademy.org/science/organic-chemistry/spectroscopy-jay/
proton-nmr/v/introduction-to-proton-nmr. Link on Canvas (Block 2).
Note that the last 2 minutes of the video gets into more detail than needed for CHEM 110.
5. NUCLEAR MAGNETIC RESONANCE (NMR)

5.1 INTRODUCTION
This spectroscopic technique has had by far the greatest impact on structure determination
for organic molecules. It provides information about the carbon and hydrogen framework of
molecules.
Certain nuclei have the property of nuclear spin and act like tiny bar magnets. Two important
nuclei with the property of nuclear spin for organic structure determination are 1H and 13C, a
stable, non-radioactive isotope of carbon.
In the absence of an external magnetic field the nuclear spins of magnetic nuclei are oriented
randomly. When nuclei with spin are placed in a magnetic field, they align themselves with
(parallel to) or against (antiparallel to) the external magnetic field. Nuclei aligned with the
magnetic field have slightly lower energy than those aligned against the field. On irradiation
with radio frequency of appropriate energy, energy is absorbed and the nuclear spin flips from
the lower energy state to the higher energy state.
applied
field
Excitation from lower

no applied field aligned to higher energy spin
(random orientation) nuclei state when E = h
The absorption frequency is different for each unique kind of 1H or 13C in any molecule. This is
because the nuclei are in different chemical, and more particularly electronic, environments.
The applied magnetic field experienced by the nucleus, and hence the ΔE for nuclear spin flip,
will depend on the shielding of the nucleus.
In an NMR spectrum the positions of absorptions are known as chemical shifts and are
measured in δ (delta) units (ppm) from the peak of a reference compound tetramethylsilane
(TMS), (CH3)4Si. TMS is defined as 0 δ.
For an NMR spectrum:

Deshielded Shielded
increasing δ
� 0δ
d

5.2 13
C NMR
All C NMR spectra considered in this course will be
13
proton decoupled spectra. Proton decoupling means

one does not observe splitting of signals which would
otherwise be seen because of 13C−1H interaction.
Consider the proton decoupled 13C NMR

spectrum of butan-2-ol:
The chemical shift range for 13C is generally δ 0 –210.

Generally, carbons bonded to electronegative substituents (O, N, halogen) will occur at higher
δ values than carbons bonded to only hydrogen or carbon. This is because the electronegative
atom pulls electrons towards itself and away from the attached carbon, whose nucleus is
deshielded.
In 13C NMR spectra sp3 carbons show signals between δ 0 – 90, whereas those for sp2 carbons
are between δ 100 – 210.
In general in 13C NMR the intensity of a signal is not an indication of the number of carbons
giving rise to a signal.
5.2.1 Problems
1. How many signals would you expect to observe in the proton decoupled 13C NMR
spectra of the following compounds?
O O O
OCH2CH3
CH3CCH3 CH3CCH2CH3 CH3COCH3
2. What structural information can you work out for a compound which has the proton
decoupled 13C NMR spectrum shown below?

Practice Question:
OH
O
B
O
C
5.3 1
H NMR
In all H NMR spectra only hydrogens give rise to absorption signals.
1
To interpret 1H NMR spectra it is necessary to consider:

1. Number of absorption signals.
2. Position of absorption signals.
3. Relative areas under absorption signals.
4. Splitting pattern for absorption signals.
5.3.1 The number of absorption signals

Hydrogens in identical molecular environments give only one absorption signal.
O
Examples (– where one signal observed): CH3CCH3 ClCH2CH2Cl
Hydrogens in ‘X’ different molecular environments give ‘X’ absorptions signals.
Two examples of identifying different molecular environments are given in the table below.
Complete the table for the remaining compounds. Label the different molecular environments
for hydrogen and state the number of absorption signals observed in the 1H NMR spectra.
Number Number of Number of

of Signals Signals Signals
CH3CH2Cl 2 CH3CH2OCH2CH3
Br
CH3CHCl2 2 CH3CH2OH

5.3.2 The position of the absorption signal
The chemical shift range for 1H is generally δ 0 – 15, with most signals observed in the δ 0 – 10
range. For hydrogen bonded to sp3 carbon, considering the signal for
C E
Examples:
C Si C C C N C O
(or halogen)
en Si 1.9 C 2.5 N 3.0 O 3.5

 value (H)
Note: Substituents containing double bonds deshield.
For hydrogen bonded to sp2 carbon
Table 2 on the next page summarises the approximate chemical shifts of hydrogens in organic
compounds. Use the table to fill in the δ range in the structures provided (next page).
5.3.3 The relative areas under absorption signals
The relative numbers of hydrogens giving rise to each signal will be given to you in tests/
exam.
Note: Where the total of these numbers does not equal the number of hydrogens in the mo-
lecular formula of the compound, each of the numbers will need to be multiplied by the same
appropriate integer.
Examples:
5 4 3 2 1 0
PPM 4 3 2 1 0
PPM


TABLE 2
1
H NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (1H NMR)
Approximate Chemical Shifts (δ) of Hydrogens in Organic Compounds
Hydrogens (H) in various δ
chemical environments (ppm downfield from TMS)
(CH3)4Si (TMS) 0
R2CHCR 1.0 (approx.)
R2CHCZ* 1.0 - 2.0
Hydrogens bonded
to sp3 carbon R2CHC=C 1.6 - 1.9
R2CHC=O 2.0 - 2.5
R2CHAr 2.5 - 3.5

R2CHX** 2.0 - 3.7
R2CHO− 3.3 - 4.5
HC=C 4.5 - 7.0

Hydrogens bonded
H−Ar 6.5 - 8.0
to sp2 carbon
HCR 9.5 - 10.0
O
HOR 3.0 - 6.0 (variable)
Hydrogen bonded HOCR 10.5 - 12.0
to oxygen
O
Notes: **X = Cl, Br, I or the N of an amine

*Z = O, C=O, or X (as defined above)
R = H or alkyl group
Two examples of δ ranges in which signals are expected for compounds are given below. For the
remaining compounds fill in, for each environment for hydrogen, the δ range in which signals
are expected.
CH3CH2Cl CH3CH2OCH2CH3 CH3CH2OCH3
d1.0-2.0 d2.0-3.7 d3.3-4.5

d1.0-2.0
O
CH3CH2OH CH3CH2COCH3

Pre-Lecture Reading - Lecture 4

Review sections 5.3, 5.3.1 “The number of absorption signals”, 5.3.2 “The position of the
absorption signal” and 5.3.3 “The relative areas under absorption signals” of the notes.
5.3.4 The splitting pattern for absorption signals

Splitting of an H absorption signal (into “lines”) occurs when on the atom that is directly bonded
to one bearing the hydrogen(s) giving rise to the absorption signal, hydrogens are attached.
C C
H H
For:
1
In general: 1 1
1 2 1
The line intensities within the split signal accord with Pascal’s triangle. 1 3 3 1
1 4 6 4 1
Complete the remainder of the table below.
‘H’ no. vicinal No. lines ‘H’ ‘H’ no. vicinal No. lines ‘H’
hydrogens signal split into hydrogens signal split into
CH3CH2Cl CH3CH2CH3
CH3
CH3CH2Cl
CH3 C CH3
CH3
CH3CH2CH3
5.3.5 The 1H NMR spectra of chloroethane and 1-chloropropane

a) chloroethane
3H
CH3CH2Cl
2H B A
A quartet at d 3.4 (H)

B triplet at d 1.5 (H).
4 3 2 1 0
PPM

b) 1-chloropropane
2H 3H
2H
4 3 2 1 0
PPM
1. The number and position of the signals.
2. The relative areas under the signals.
3. The splitting pattern for the signals.
Practice Question:
O
A
HO
O
B
O
O
O C

6. SPECTROSCOPY SUMMARY
MS Ion of heaviest mass (molecular ion) corresponds to the molar mass.
Compounds with the same molecular formula have a molecular ion with the same mass.
IR Different bonds show absorption bands at different wavenumbers.

Particularly distinctive absorptions – refer data sheet.
Compounds with the same functional group have similar spectra.
Generally IR used to distinguish between compounds containing different functional
groups.
UV-VIS Absorption of radiation corresponds to electronic excitation.

Generally observed for compounds having π-bonds.
Compounds with only σ-bonds are transparent to UV-VIS.
Compounds with ‘isolated’:
C=C(s) λmax approx. 170 nm (π - π* electron transition)
C=O(s) λmax approx. 170 nm AND λmax approx. 280 nm (n - π* electron transition)
Compounds with conjugated double bonds absorb at longer wavelength. The more
extensive the conjugation within a molecule the longer the wavelength for the longest
wavelength absorption.
Beer’s Law: A = εbc [A = absorbance, b = path length (cm),
ε = molar absorptivity (L mol−1 cm−1), c = concentration (mol L−1)]
NMR Signals for both 13C and 1H are recorded in units of δ (ppm) from TMS, which is
assigned a value of 0 δ.
13
C: In 13C NMR spectra only carbons give absorption signals.
Each unique carbon will give a different signal.
Generally signals for sp3 carbons are between 0 – 90 δ, whereas those for sp2 carbons
are between 100 – 200 δ.
1
H: In 1H NMR spectra only hydrogens give absorption signals.
a) The number of absorption signals equals the number of non-identical molecular
environments for hydrogen in the molecule.
1. Note that mono-substituted benzene ring protons usually appear as
one signal with a relative area under the peak of 5 protons.
b) The position of absorption signals depends on the molecular environment of
hydrogen(s). (Positions (δ values) see data sheet.)
c) The relative areas under absorption signals corresponds to the relative numbers
of hydrogens giving the absorption signals.
d) The splitting pattern for a signal, that is the number of “lines”, depends on the
number of vicinal/neighbouring hydrogens. (N+1 rule)

7. STRUCTURE DETERMINATION FROM SPECTROSCOPIC DATA
7.1 ESTABLISHING THE FUNCTIONAL GROUP(S) PRESENT
A good general strategy is: Empirical formula

↓
Molecular formula
↓
Elemental Double Bond Equivalents
Composition 0 1 2 >4
Phenyl
C, H, (halogen)
C, H, O
C, H, N
C, H, N, O
IR distinguishes alcohol from ether

acid from ester
3° from 1° and 2° amine
1
H NMR distinguishes aldehyde from ketone
Note: For 4 or more double bond equivalents assume a, or if appropriate more than one,
‘phenyl’ group is present. (Check the 1H NMR for signals between δ 6.5 – 8.0 to establish the
number of substituents on the aromatic ring.) Then bearing in mind the molecular formula,
account for any remaining double bond equivalents in terms of an appropriate functional group
or combination of functional groups.
Examples: (Possibilities based on mono-substituted aromatic ring and one functional group.)
C7H6O2
4 D/U 1 D/U O O
(C6H5) + CHO2 OCH or COH
ester or
carboxylic acid

C8H10O
4 D/U 0 D/U OH
(C6H5) + C2H5O OCH2CH3 or CHCH3
alcohol or ether
or........

Question 1.
For the compounds, molecular formula C9H10O3, below:
(a) Which compound, if any, can be distinguished from the others by

(i) (3 marks) the molecular ions in their mass spectra.
Justify your choice. A B C D E None
(Circle one.)
(ii) (3 marks) their IR spectra. A B C D E None

Justify your choice. (Circle one.)
(iii) (3 marks) their UV-VIS spectra.

Justify your choice. A B C D E None
(Circle one.)
(iv) (3 marks) the number of signals at > 100δ in their A B C D E None

proton decoupled 13C NMR spectra. (Circle one.)
Justify your choice.
(b) (i) Which compound has a signal in the

1
H NMR split into four lines, at δ3.9? A B C D E None
Justify your choice. (Circle one.)
(ii) The area of this signal corresponds to __________ hydrogens.
(c) (3 marks) Which compound has an unsplit signal in the 1H NMR corresponding to six
hydrogens? __________
Justify your choice.

Post-Unit Reading - A Worked Example

This section uses a compound, molecular formula C10H13NO [DBEs = 5], which is known to
be a primary amide with a phenyl group to illustrate a stepwise procedure for structure
determination.
4 DBE O 1 DBE
CNH2
i) Subtract the atoms accounted for from the molecular formula.
Our example: amide group CONH2 original molecular formula C10H13NO
phenyl group C6H5 accounted for: C7 H7 NO
atoms not accounted for: C3H6
ii) Consider if the remaining carbons must be joined together or whether they may be
split into two fragments. In our example, where each of the phenyl and amide has only
one unsatisfied valence they must be joined together. For a functional group with two
unsatisfied valences they could be split into two fragments. Draw the possible isomers
for the remaining carbon fragment(s). Don’t forget branched chains.
Our example:
CH3 CH2 CH3 CH3
CH2 CH2CH2 CHCH2 CH C
CH3
iii) Connect the fragments to draw the possible constitutional isomers.
Our example:
CH3 CH3
Ph CH2CH2CH2CONH2 Ph CHCH2CONH2 PhCH2CHCONH2
1 CH3 2 3
CH2CH3
Ph CCONH2 Ph CHCONH2
CH3 4 5
iv) Look at the 1H NMR spectrum and assign absorption signals due to the known fragments.
Our example: The five aromatic ring hydrogens and the two amide hydrogens.
v) Consider the remaining absorption signals. The number of absorption signals equals the
remaining number of non-equivalent hydrogen environments.
Our example: Compounds 1, 2, 3 and 5 have three additional environments. Compound 4
has one. Hence we can distinguish 4 from the other based on the number of signals.
vi) Where the number of absorption signals does not allow differentiation, consider the ratio
of areas of these signals.
Our example:
1 2 : 2 : 2 2 3 : 2 : 1
3 1 : 3 : 2 5 1 : 3 : 2
1 can be distinguished from 2, 3 and 5.

vii) To distinguish between the remaining constitutional isomers consider chemical shifts in
association with areas and splitting patterns of the absorption signals.
Our example:
In the range 2.0 – 2.5 [R2CHC= ] the area for 3 and 5 =
1H, but for 2 = 2H. For 3 signal is split into 6 lines, but for
5 is 3 lines.
Notes:
1. Other than 5 Hs giving rise to a signal in the aromatic region, greater than 3 Hs giving rise
to an absorption signal is an indication of some symmetry within the molecule.
2. For molecular formulae where the number of carbons does not exceed three it is best to
draw out the constitutional isomers and assess which are possible on the basis of the
number of absorption signals observed in the 1H NMR spectrum.
For example: C3H6Br2 whose 1H NMR spectrum is given below.

Constitutional No. of 1H NMR
isomers signals
CH3CH2CHBr2 3
2H
CH3CHCH2Br 3
1H
Br
CH2BrCH2CH2Br 2
CH3CBr2CH3 1
4 3 2 1 0δ
PPM
2 signals Full interpretation: H H
Position (expect) δ 2.0 – 3.7 δ 1.0 – 2.0
∴CH2BrCH2CH2Br
(actual) δ3.5 δ 2.3
Areas (2H:1H ×2) 4H 2H
Splitting: vic Hs 2 4
∴ observe 3 lines 5 lines

REVISION EXERCISES FOR PART 2 OF BLOCK 2
1. For each of the molecular formulae given below, draw the structural formula of a
constitutional isomer which would show only one unsplit signal in its 1H NMR spectrum.
a) C5H12 b) C2H6O c) C3H6O d) C3H6Cl2 e) C4H9Cl
2. For each of the compounds given below state how many absorption signals would be
found in their proton decoupled 13C NMR spectra.
O
a) b) (CH3)2CHCl c) (CH3)2C=CH2 d) CH3CO2CH3
CH3CCH3
e) CH3CH2CO2H f)
O g) CH2CHO
CH3CC(CH3)3
3. With respect to the 1H NMR spectra of each of the compounds in Q2 above state:
i) the number of absorption signals which would be seen.
ii) the δ position at which each signal would be found.
iii) the relative areas under the absorption signals.
iv) the number of lines into which each absorption signal would be split.
Note: For compound g) the five aromatic hydrogens can be regarded as giving rise to a single
absorption signal in the 1H NMR spectrum, and no discussion of splitting of this signal is
required.
4. Assume you are carrying out the dehydration of 1-methylcyclohexanol to yield an alkene.
How could IR spectroscopy be used to determine when the reaction is complete?
Two alkenes are obtained in the above reaction. Explain briefly how the 1H NMR spectra
of these two products would differ.
5. For each of the compounds whose structures and 1H NMR spectra are given below:
i) state any characteristic absorptions which would be found in their IR and/or
UV-VIS spectra.
ii) state the value at which M+• would be found in their mass spectra.
iii) give a full interpretation of their 1H NMR spectra.

Compound A (CH3CH2)3N

4 3 2 1 0
PPM
O
Compound B
HCOCH3
9 8 7 6 5 4 3 2 1 0
PPM

6. For each of compounds C and D determine the structure of the compound from the
spectral information given below and give a full interpretation of the spectral data.
Where spectral information is not available indicate what you would expect to observe.
Compound C Signal centred at

d 1.15 is split into 2 6H
Empirical formula C3H4
lines.
MS: molecular ion at mass 120
IR: not available
UV: λmax = 208 nm
NMR: 13C – not available
1H – shown to the right
Signal centred at
5H d 2.90 is split into 7 1H
lines.
8 7 6 5 4 3 2 1 0
PPM
Compound D
Molecular formula C2H4O2
UV: λmax = 280 nm
IR: see right
NMR: 13C (proton decoupled)– two signals
1
H – as tabulated below
signal position signal area signal splitting

δ 2.1 3H none observed
δ 11.8 1H none observer
7. Structures for three compounds, X, Y and Z, with the molecular formula C6H12Cl2O2 are:
Cl Cl Cl
(CH3CH2O)2CCH2Cl (CH3CH2O)2CHCHCl2 CH3CH2OCHCHOCH2CH3
X Y Z
i) Could these three compounds be distinguished on the basis of the mass of their
molecular ions in their mass spectra? Justify your answer.
ii) The 1H NMR spectrum of one of the above compounds is summarised below.
signal position signal area signal splitting
δ 1.25 6H 3 lines
δ 3.75 4H 4 lines Sketch the 1H NMR spectrum.
δ 4.50 1H 2 lines
δ 5.50 1H 2 lines
Which of the compounds would give this 1H NMR spectrum?

Justify your answer, giving a full interpretation of the 1H NMR spectrum.
iii) Could compounds X, Y and Z be distinguished from each other on the basis of the
number of absorption signals present in their proton decoupled 13C NMR spectra?
Justify your answer.

CHEM 110 SPECTROSCOPY DATA SHEET
TABLE 1
IMPORTANT INFRARED ABSORPTION REGIONS
(STRETCHING FREQUENCIES)
Bond Present ν (cm 1)
−
O−H (alcohol, phenol) 3700 – 3200

(carboxylic acid) 3600 – 2500 (broad)
N−H 3500 – 3100
C−H 3100 – 2800
C=O 1850 – 1600
C=C (aliphatic) 1680 – 1600
(aromatic) 1620 – 1550
C−O 1250 – 1050 (less definitive)
TABLE 2
1
H NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (1H NMR)
Approximate Chemical Shifts (δ) of Hydrogens in Organic Compounds
Hydrogens (H) in various δ
chemical environments (ppm downfield from TMS)
(CH3)4Si (TMS) 0
R2CHCR 1.0 (approx.)
R2CHCZ* 1.0 - 2.0
Hydrogens bonded
R2CHC=C 1.6 - 1.9
to sp3 carbon
R2CHC=O 2.0 - 2.5
R2CHAr 2.5 - 3.5

R2CHX** 2.0 - 3.7
R2CHO− 3.3 - 4.5
HC=C 4.5 - 7.0

Hydrogens bonded
H−Ar 6.5 - 8.0
to sp2 carbon
HCR 9.5 - 10.0
O
HOR 3.0 - 6.0 (variable)
Hydrogen bonded HOCR 10.5 - 12.0
to oxygen
O
Notes: **X = Cl, Br, I or the N of an amine

R = H or alkyl group
*Z = O, C=O, or X (as defined above)

Block 2 Spectros

Uploaded by

Copyright:

Available Formats

Block 2 Spectros

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Block 2 Spectros

Uploaded by

Copyright:

Available Formats

CHEM110/Block 2/Spectroscopy/2020 1

Lecturer: Dr Melissa Cadelis

This handout should be brought to all lectures.

Laboratory Day and Time: Bench Number:

At the end of this block you should be able to:

© School of Chemical Sciences The University of Auckland

Pre-Lecture Reading Lecture 1

This course introduces the following spectroscopic techniques:

The fundamental importance of molecular spectroscopy is that absorption of radiation of

© School of Chemical Sciences The University of Auckland

Therefore, we would observe an energy absorption at ΔE = hν

The spectrum of a compound is a ‘graph’ of the fraction of radiation absorbed or transmitted

© School of Chemical Sciences The University of Auckland

CH3CH2CH2OCH3 CH3CH2CH2OH (CH3)2CHOCH3

© School of Chemical Sciences The University of Auckland

Such bond vibrations are either stretching:

O−H (alcohol, phenol) 3700 – 3200

© School of Chemical Sciences The University of Auckland

ii) As a ‘fingerprint’, as no two compounds have identical spectra.

© School of Chemical Sciences The University of Auckland

Pre-Lecture Reading Lecture 2

Ultraviolet-visible radiation is of appropriate energy to raise electrons in some molecules

When discussing UV-VIS spectroscopy, an important structural feature, conjugation, of some

© School of Chemical Sciences The University of Auckland

UV-VIS spectrum is a plot of absorbance (Y-axis)

Compounds containing only σ-bonds are generally transparent to UV-VIS light.

Note: ΔE n → π* < ΔE π → π* and so the absorption for n → π* is at longer λ than π → π*.

© School of Chemical Sciences The University of Auckland

3.2 UV-Vis and Beer’s (Beer-Lambert’s) Law

For a particular compound at a specified λ:

© School of Chemical Sciences The University of Auckland

3.2.1 Utility of Beer’s Law

Then at the same wavelength determine the absorbance x

© School of Chemical Sciences The University of Auckland

Consider the following:

ii) A compound with a molecular formula of C5H10 has DBE = 1.

Using either UV-VIS or IR spectroscopy it can be determined whether the compound is

iii) A compound has the molecular formula C3H8O.

© School of Chemical Sciences The University of Auckland

7. A compound is known to be mono-functional; that is it contains one functional group.

© School of Chemical Sciences The University of Auckland

Pre-Lecture Reading Lecture 3

5. NUCLEAR MAGNETIC RESONANCE (NMR)

Excitation from lower

For an NMR spectrum:

© School of Chemical Sciences The University of Auckland

proton decoupled spectra. Proton decoupling means

Consider the proton decoupled 13C NMR

The chemical shift range for 13C is generally δ 0 –210.

© School of Chemical Sciences The University of Auckland

To interpret 1H NMR spectra it is necessary to consider:

5.3.1 The number of absorption signals

Hydrogens in ‘X’ different molecular environments give ‘X’ absorptions signals.

Number Number of Number of

© School of Chemical Sciences The University of Auckland

en Si 1.9 C 2.5 N 3.0 O 3.5

Note: Substituents containing double bonds deshield.

For hydrogen bonded to sp2 carbon

5.3.3 The relative areas under absorption signals