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• 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.
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
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.
Vertical axis Absorbance the stronger the absorbance the larger the peak
• 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
• 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!
O-H STRETCH
AND
CARBOXYLIC
ACID
C=O STRETCH
CHARACTERISTIC FREQUENCIES
A. molecular mass
B. bonds present
C. total number of protons
D. total number of proton environments
IR Spectra interpretation
Practice
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
3 2 3
How would you use low resolution NMR to distinguish
between the isomers propanone and propanal?
Below: 1H NMR
What a low resolution NMR spectrum tells you
Low Resolution High Resolution
Remember: In a high resolution spectrum,
The number of peaks tells the low resolution spectrum are
you the number of different
environments the hydrogen split into clusters of peaks.
atoms are in. 1 peak a singlet
The ratio of the areas under
the peaks tells you the ratio 2 peaks in the cluster a doublet
of the numbers of hydrogen
atoms in each of these 3 peaks in the cluster a triplet
environments. 4 peaks in the cluster a quartet
The chemical shifts give you
important information about The amount of splitting of the
the sort of environment the peaks gives you important extra
hydrogen atoms are in. 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).
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
# 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
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
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.