• IHD

• IR Spectroscopy
• Mass Spectroscopy
• NMR
11.3: Analytical techniques can be used to determine the structure
of a compound, analyze the composition of a substance, or
determine the purity of a compound. Spectroscopic techniques are
used in the structural identification of organic and inorganic
compounds.

20.1: Although spectroscopic characterization techniques form the

backbone of structural identification of compounds, typically no
one techniques results in a full structural identification of a
molecule
Analytical techniques
 Qualitative analysis: detection of presence but not
quantity of substance in mixture
 Quantitative analysis: measurement of the quantity of
a particular substance in a mixture
 Structural analysis: description of how atoms are
arranged in molecular structures
Index of Hydrogen Deficiency
Learning outcomes
 Understand how the number of double bonds/rings
can be worked out from molecular formula
Index of Hydrogen Deficiency
 Alkanes have maximum number of hydrogen atoms
 For every two hydrogen atoms fewer than in alkane
with same number of carbon atoms, there is one
double bond or ring present. (double bond equivalent)
 The number of double bond equivalents sometimes
called degree of unsaturation or the Index of
hydrogen deficiency.
How the index of hydrogen
deficiency works.
 1 A double bond and ring each counts as one IHD.
 2 A triple bond counts as two IHD
Hydrocarbons (CxHy):
IHD=1/2[2C+2-H]
(where x = number of carbon, Y= number of hydrogen)
 Example C4H8
½(8+2-8)= 1
Compounds Containing Elements
Other than C and H
 O and S atoms do not affect the IHD.
 Halogens (F, Cl, Br, I) are treated like H atoms
(CH2Cl2 has the same IHD as CH4).
 For each N, add one to the number of C and one to the
number H (CH5N is treated as C2H6. CH4N2O is
treated as C3H6 by adding 2 to # of C and 2 to # of H).
Calculate IHD for
 C3H5N will be treated as C4 H6
 IHD = 1/2(4x2 + 2- (6) = 4/2=2
 Possible structures
Calculate IHD for
 C6H9Cl will be treated like C6H10
 IHD=1/2[2C+2-H]
 IHD =1/2[12+2-10]=4/2=2
Practice problems
IHD = 3

CH3CHCHCH2CHCH2 IHD = 2

IHD = 5

IHD = 1

CH3C≡CCOCH3
IHD = 3
Learning outcomes
 Understanding
 Mass spectrometry (MS), proton nuclear magnetic
resonance spectroscopy (1H NMR) and infrared
spectroscopy (IR) are techniques that can be used to
help identify compounds and to determine their
structure.

Learning outcome
Understanding
 Mass spectrometer is a technique that can help in
identifying structure of organic compounds
Application and skills
 Deduction of information about the structural features
of a compound from percentage composition data,
MS, 1H NMR or IR.
Mass spectrometer

Picture Source http://chemistry.umeche.maine.edu/CHY251/Ch13-Overhead4.html

Using a mass spectrum to find
relative formula mass
 The formation of molecular ions
 When the vaporized organic sample passes into the
ionization chamber of a mass spectrometer, it is
bombarded by a stream of electrons. These electrons
have a high enough energy to knock an electron off an
organic molecule to form a positive ion. This ion is
called the molecular ion.
 The molecular ion is often given the symbol M+ or M•-
the dot in this second version represents the fact that
somewhere in the ion there will be a single unpaired
electron. That's one half of what was originally a pair
of electrons - the other half is the electron which was
removed in the ionization process.
 The molecular ions tend to be unstable and some of
them break into smaller fragments. These fragments
produce the familiar stick diagram. Fragmentation is
irrelevant at this stage.
Using the molecular ion to find
the relative formula mass
 In the mass spectrum, the heaviest ion (the one with
the greatest m/z value) is likely to be the molecular
ion.
 For example, in the mass spectrum of pentane, the
heaviest ion has an m/z value of 72.

Analyzing mass spectrometer data
C3 H 8
MS data of N,N-diethylmethylamine
Learning outcome
Understanding
 Infrared spectroscopy is a technique that can help in
identifying structure of organic compounds
Application and skills
 Deduction of information about the structural features
of a compound from percentage composition data,
MS, 1H NMR or IR.
WHAT IS AN INFRA-RED
SPECTRUM?
 If a range of infra-red frequencies shine at an organic
sample, some of the frequencies get absorbed by the
compound. A detector attached to the other end of
spectrum measured frequencies absorbed or
transmitted.
 How much of a particular frequency gets through the
compound is measured as percentage
transmittance.

What an infra-red spectrum looks like
A graph is produced showing how the percentage transmittance varies
with the frequency of the infra-red radiation.
Analyzing IR spectrum
 IR spectra are not particularly easy to analyse, nor do
they give definitive information about structure. There
are however, two different stages in an analysis.
 1 Identification of absorptions
 2 Fingerprinting
 The first stage involves looking for characteristic
absorptions and attempting to ascribe them to specific
structural features. The second stage is usually carried
out after a series of analyses leads to a possible
conclusion.
 INFRA RED SPECTRA - USES

IDENTIFICATION OF The presence of bonds such as O-H

PARTICULAR BONDS and C=O within a molecule can be
IN A MOLECULE confirmed because they have
characteristic peaks in identifiable
parts of the spectrum.

IDENTIFICATION OF The only way to completely identify

COMPOUNDS BY DIRECT a compound using IR is to compare
COMPARISON OF SPECTRA its spectrum with a known sample.
The part of the spectrum known as
the ‘Fingerprint Region’ is unique to
each compound.
 INFRA RED SPECTRA - INTERPRETATION

Infra-red spectra are complex due to the many vibrations in each molecule.
Total characterisation of a substance based only on its IR spectrum is almost
impossible unless one has computerised data handling facilities for comparison of
the obtained spectrum with one in memory.
However, the technique is useful when used in conjunction with other methods
such as nuclear magnetic resonance (nmr) spectroscopy and mass spectroscopy.

Peak position depends on bond strength

masses of the atoms joined by the bond

strong bonds and light atoms absorb at lower wavenumbers

weak bonds and heavy atoms absorb at high wavenumbers

 INFRA RED SPECTRA - INTERPRETATION

Vertical axis Absorbance the stronger the absorbance the larger the peak

Horizontal axis Frequency wavenumber (waves per centimetre) / cm-1

Wavelength microns (m); 1 micron = 1000 nanometres
 FINGERPRINT REGION

• organic molecules have a lot of C-C and C-H bonds within their structure
• spectra obtained will have peaks in the 1400 cm-1 to 800 cm-1 range
• this is referred to as the “fingerprint” region
• the pattern obtained is characteristic of a particular compound the frequency
of any absorption is also affected by adjoining atoms or groups.
 IR SPECTRUM OF A CARBONYL COMPOUND

• carbonyl compounds show a sharp, strong absorption between 1700 and 1760 cm-1
• this is due to the presence of the C=O bond
 IR SPECTRUM OF AN ALCOHOL

• alcohols show a broad absorption between 3200 and 3600 cm-1

• this is due to the presence of the O-H bond
 IR SPECTRUM OF A CARBOXYLIC ACID

• carboxylic acids show a broad absorption between 3200 and 3600 cm-1
• this is due to the presence of the O-H bond
• they also show a strong absorption around 1700 cm-1
• this is due to the presence of the C=O bond
 IR SPECTRUM OF AN ESTER

• esters show a strong absorption between 1750 cm-1 and 1730 cm-1
• this is due to the presence of the C=O bond
WHAT IS IT!

One can tell the difference between alcohols, aldehydes

and carboxylic acids by comparison of their spectra.

O-H STRETCH ALCOHOL

C=O STRETCH ALDEHYDE

O-H STRETCH

AND
CARBOXYLIC
ACID
C=O STRETCH
CHARACTERISTIC FREQUENCIES

N-H CN C-Cl

O-H C=O C-O

C-H Aromatic C-C

C=C C-C alkanes

CHARACTERISTIC ABSORPTION FREQUENCIES

Bond Class of compound Range / cm-1 Intensity

C-H Alkane 2965 - 2850 strong
C-C Alkane 1200 - 700 weak
C=C Alkene 1680 - 1620 variable

C=O Ketone 1725 - 1705 strong

Aldehyde 1740 - 1720 strong
Carboxylic acid 1725 - 1700 strong
Ester 1750 - 1730 strong
Amide 1700 - 1630 strong
C-O Alcohol, ester, acid, ether 1300 - 1000 strong

O-H Alcohol (monomer) 3650 - 3590 variable, sharp

Alcohol (H-bonded) 3420 - 3200 strong, broad
Carboxylic acid (H-bonded) 3300 - 3250 variable, broad

N-H Amine, Amide 3500 (approx) medium

CN Nitrile 2260 - 2240 medium

C-X Chloride 800 - 600 strong

Bromide 600 - 500 strong
Iodide 500 (approx) strong
Which feature of a molecule does infrared
spectrometry detect?

A. molecular mass
B. bonds present
C. total number of protons
D. total number of proton environments
IR Spectra interpretation
Practice

New Data booklet

Table 26
i

iii

ii
Answer
Practice
 Page 551 Q 14 part a
Further Practice
 https://www2.chemistry.msu.edu/faculty/reusch/virtt
xtjml/questions/Spectroscopy/irmsprb/infrared.htm
Nuclear Magnetic Resonance
Learning outcome
Understanding
 NMR spectroscopy is a technique that can help in
identifying structure of organic compounds
Application and skills
 Deduction of information about the structural features
of a compound from percentage composition data,
MS, 1H NMR or IR.
NMR
 Nuclear magnetic resonance relies on the magnetic
field produced by a spinning nucleus containing an
odd number of nucleons (protons or neutrons). In the
presence of an external magnetic field the nucleus can
exhibit more than one spin state and can move
between these states by the absorption of
electromagnetic radiation of a specific frequency
(energy).
 The energy absorbed can be detected and from this
information about the location (environment) of the
nucleus can be deduced.
NMR is probably the most useful tool in the
organic chemists arsenal for structural
determination.
 As organisms are mainly water (containing H atoms
with an odd number of nucleons), NMR has developed
into an invaluable medical diagnostics tool, called an
MRI (magnetic resonance instrument) scan.
Nuclear magnetic resonance
 This tells us the number of hydrogen atoms in
different environments within the molecule. As
hydrogen is present in (almost) all organic compounds
this technique is very useful. The pattern produced by
the hydrogen atoms is often split into finer structure,
that also gives information about the number of
hydrogen adjacent to the absorbing atoms.
Low resolution NMR
 A low resolution spectrum looks much simpler
because it can't distinguish between the individual
peaks in the various groups of peaks

The numbers against the peaks represent the

relative areas under each peak. That information
is extremely important in interpreting the spectra
Interpreting L R NMR spectrum
Three peaks in the spectrum
corresponds to different
chemical environments of H
atoms
Different sizes of peak give
valuable information
 Are underneath a peak is
proportional to number of
hydrogen atoms in that
environment.
 Area underneath peaks can
be worked out by integration
trace. The vertical heights of
the steps in Integration trace
are proportional to the
number of hydrogen atoms
in each envirnoment.
Interpreting L R NMR spectrum
Chemical Shift: The
Horizontal scale on NMR, is
given by the symbol δ has a
unit parts per million ppm.
 The Chemical Shift gives
information about the
environment of protons(
Hydrogen atoms). The
protons in different
chemical environment
give different chemical
shift
 Detail about chemical
shift will be covered in
HL syllabus.
NMR Spectrum of Pentan-3-one
 Symmetrical molecule
 Two peaks show two
different chemical
environment
 Heights of peaks as ratio
of 2;3 in integration
trace, show four H atom
in one environment and
6 in other.
Identify number of different chemical
environments and ratio of H atoms in each
environment

3 2 3
How would you use low resolution NMR to distinguish
between the isomers propanone and propanal?

One Peak 3 peaks

CH3CH2COOH.
HL
Chemical Shift ( HL only)
 The horizontal scale on a nuclear magnetic resonance
spectrum is called chemical shift.
 The symbol for chemical shift is δ.
 It is measured as parts per million
 The Chemical Shift gives information about the
environment of protons( Hydrogen atoms). The
protons in different chemical environment give
different chemical shift
 Chemical shift are measured relative to TMS
 Chemical shift for TMS is Zero
 https://www.youtube.com/watch?v=k0eR8YqcA8c
 https://www.youtube.com/watch?v=OrvAUDgVoT8&f
eature=iv&src_vid=k0eR8YqcA8c&annotation_id=ann
otation_877622
Tetramethylsilane is the standard
 All Hs are the same = 1
signal
 Si
 Has lower EN than
Carbon
 Si absorbs in a different Si(CH3)4
part of the spectrum Has low boiling point
than C when bonded to Is chemically inert (non-
H reactive)
Is soluble in most organic
solvents
Chemical Shift values relative to TMS
Values are given in data book let page 26, table 27
Using Chemical Shift
High-resolution 1H NMR
 Can show the difference in the spins of nuclei
 Right: Hi-res 1H NMR

 Below: 1H NMR
What a low resolution NMR spectrum tells you
Low Resolution
 Remember:
 The number of peaks tells
you the number of different
environments the hydrogen
atoms are in.
 The ratio of the areas under
the peaks tells you the ratio
of the numbers of hydrogen
atoms in each of these
environments.
 The chemical shifts give you
important information about
the sort of environment the
hydrogen atoms are in.
High Resolution
 In a high resolution spectrum,
the low resolution spectrum are
split into clusters of peaks.
 1 peak a singlet
 2 peaks in the cluster a doublet
 3 peaks in the cluster a triplet
 4 peaks in the cluster a quartet
 The amount of splitting of the
peaks gives you important extra
information.
Interpreting a high resolution spectrum
 The n+1 rule
 The amount of splitting tells you about the number of
hydrogens attached to the carbon atom or atoms next door
to the one you are currently interested in.
 The number of sub-peaks in a cluster is one more than the
number of hydrogens attached to the next door carbon(s).

 Singlet next door to carbon with no hydrogens attached

 doublet next door to a CH group
 triplet next door to a CH2 group
 quartet next door to a CH3 group
Multiplicity (Splitting)
• NEIGHBOR hydrogens = number of peaks -1
Multiplicity (Splitting)
3 peaks (triplet) 300 MHz ¹H NMR 3 peaks (triplet)
In C DC l 3
2 neighbor H’s 2 neighbor H’s 1 .2
(probably CH2) (CH2) 1 .1

1 .0

0 .9
6 peaks (hextet) 0 .8
5 H’s 0 .7
(CH3 & CH2) 0 .6

0 .5

0 .4

0 .3

0 .2

0 .1

0 .0

-0 .1
3 .5 3 .0 2 .5 2 .0 1 .5 1 .0
© Si g m a -Al d ri c h C o .
AL L R IGHT S R E SE R VE D
Chemical shift 4.1 2.1 1.3
# of protons in environments 2 3 3
Splitting Quartet Singlet triplet
Multiplicity 4 1 3
# of protons on adjacent C atoms 3 0 2
 Deduce the structure formula of given compound. The molcular formula of
the compound is C4H8 O

Chemical shift 2.4 2.1 1.1

# of protons in environments 2 3 3
Splitting Quartet Singlet triplet
Multiplicity 4 1 3
# of protons on adjacent C atoms 3 0 2
Practice Example
 11.7 page 542
Calculate # H’s for each peak
C3H7Cl

300 MHz ¹H NMR

In C DC l 3
1 .2

1 .1

1 .0

0 .9

0 .8

0 .7

0 .6

0 .5

0 .4

0 .3

0 .2

0 .1

0 .0

-0 .1
3 .5 3 .0 2 .5 2 .0 1 .5 1 .0
© Si g m a -Al d ri c h C o .
AL L R IGHT S R E SE R VE D
Calculate # H’s for each peak
C3H7Cl

300 MHz ¹H NMR

In C DC l 3
1 .2

1 .1

1 .0

0 .9

0 .8

0 .7

0 .6

0 .5

0 .4

0 .3

0 .2

0 .1

0 .0

-0 .1
3 .5 3 .0 2 .5 2 .0 1 .5 1 .0
© Si g m a -Al d ri c h C o .
AL L R IGHT S R E SE R VE D

2H 2H 3H
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

1.0
H
| 0.9
─C─
0.8
|
H 0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

1.0
H
| 0.9
─C─
0.8
CH |
2 H 0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

1.0
H
0.9
Funct. Grp.

|
─C─
0.8
CH |
2 H 0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

H 1.0
Funct. Grp.

X- |
─C─ 0.9
CH |
2 H 0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

H 1.0
Funct. Grp.

X- |
─C─ H 0.9
CH | |
2 H ─C─ 0.8
|
0.7
H
0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

H 1.0
Funct. Grp.

X- |
─C─ H 0.9
CH | |
2 H ─C─ 0.8
CH3
|
0.7
H
0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

1.0
H
| 0.9
X- ─C─
Funct.

H
Grp.

CH | CH 0.8
| 2
2 H
─C─ 0.7
CH3
|
H 0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1
H
| 1.0
H H─C─
| | 0.9
X- ─C─ H
Funct.

H
Grp.

CH | CH 0.8
| 2
2 H
─C─ 0.7
CH3
|
H 0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1
H
CH
| 2 1.0
H H─C─
| | 0.9
X- ─C─ H
Funct.

H
Grp.

CH | CH 0.8
| 2
2 H
─C─ 0.7
CH3
|
H 0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
Make NMR Mosaic Pieces: C3H7Cl
300 MHz ¹H NMR
In C DC l 3
1.2

1.1

H H H 1.0
CH CH
| 2 | 2 | X- 0.9
H─C─ ─C─ ─C─

Funct.
Grp.
| | CH |
CH3 0.8
H H 2 H
0.7

0.6
1-chloropropane 0.5

0.4

0.3

0.2

0.1

0.0

-0.1
3.5 3.0 2.5 2.0 1.5 1.0
© Si g m a -Al dri c h C o .
AL L R IGHT S R E SE R VE D
HL
Learning outcomes
 Understanding
 The structural technique of single crystal X-ray
crystallography can be used to identify the bond
lengths and bond angles of crystalline compounds.
Introduction
 X-ray crystallography is the oldest and most precise
method.
 Crystallography in which a beam of X-rays strikes a
single crystal, producing scattered beams.
 When they land on a piece of film or other detector,
these beams make a diffraction pattern of spots; the
strengths and angles of these beams are recorded as
the crystal is gradually rotated.
 Each spot is called a reflection, since it corresponds to
the reflection of the X-rays from one set of evenly
spaced planes within the crystal.
Computational analysis
 The data is analysised by computer and combined with
other data to refine a model of the arrangement of
atoms within the crystal. The final, refined model of
the atomic arrangement - now called a crystal
structure - is usually stored in a public database.
Information obtained
 Single-crystal X-ray Diffraction is a non-destructive
analytical technique which provides detailed
information about the internal lattice of crystalline
substances, including unit cell dimensions, bond-
lengths, bond-angles, and details of site-ordering.
 Directly related is single-crystal refinement, where the
data generated from the X-ray analysis is interpreted
and refined to obtain the crystal structure.
 Crystallography is the most unambiguous method for
determining structures of small molecules and
macromolecules.