Modern analytic techniques [MAT]: mass
spectroscopy and deducing structures DATE: TUE
• Today’s work can be found on the VLE. 4th
• Work through the PowerPoints running March
them as a slideshow. NEEDED
2025
• Show evidence of work for today’s lesson TODAY:
and get your work checked. LAPTOPS
• REFER to TEXTBOOK CHAPTER 7.1 Mass
spectroscopy pages 216 - 220 +
notebooks
Y12 Organic 1 and MAT 1 test: Sunday
9th March
Instructions:
1 The PowerPoint contains the key
information for today’s lesson
together with some activities to try.
Run the presentation as a slideshow.
2. This booklet will be issued during
class time.
Tuesday 4th March 2024
Modern analytic techniques
[MAT]: Infra-red spectroscopy
and deducing structures
Before you start it would be
helpful to know the names
and structures of organic
functional groups
Nodule Nugget of wisdom
Improvements in modern instrumentation have led to advances in spectroscopic techniques (IR,
Nature of science 1HNMR and MS) and have resulted in detailed knowledge of the structure of compounds.
Although spectroscopic characterization techniques form the backbone of structural identification
Essential idea of compounds, typically no one technique results in a full structural identification of a molecule
Directory of analytic techniques
Analytic technique Abbreviation Description
Infra-red spectroscopy IR Shows the functional groups in an organic compound
Proton nuclear 1 H NMR Provides information about the carbon–hydrogen framework of a
magnetic resonance compound
i) Finding the molecular formula of a compound by measuring the
mass of its molecular ion to a high degree of accuracy.
Mass spectrometry MS
ii) Deducing the structure of a molecule by looking at the fragments
produced when a molecular ion fragments inside a mass spectrometer
X-ray crystallography XRC Used to identify the bond lengths and bond angles of crystalline
compounds
The different types of energy
Interaction of radiation with matter associated with a hydrogen
chloride molecule
• When electromagnetic radiation interacts
with molecules, the molecules absorb
energy and this can cause a variety of
changes, as shown for HCl
• Which changes occur depends on the
molecule and the energy of the
electromagnetic radiation.
• Molecules can absorb only certain
discrete amounts of energy due to the
quantization of their energy levels.
• There are separate energy levels, with
fixed energy gaps or differences between
them, for each type of change
Interaction of radiation
with matter
• Molecules can absorb only certain discrete amounts of
energy due to the quantization of their energy levels.
• There are separate energy levels, with fixed energy gaps
or differences between them, for each type of change.
To change the energy of a molecule from E1 to E2 , photons of
electromagnetic radiation must provide a specific energy equal
to the energy difference, (E2 – E1 ).
The vibrational and
This shows an
rotational energy levels
increase in energy level
in a molecule
from E1 to E2 resulting
from absorption of a
photon of energy hf
The energy absorbed by Term Definition
the molecule can change Infrared radiation Electromagnetic radiation with
its electronic, wavelength longer than that of red light
but shorter than that of radio waves.
vibrational or nuclear
•
energy. Infrared Absorption spectroscopy carried out in
Infrared radiation causes covalent bonds to spectroscopy the infrared region of the
electromagnetic spectrum, detecting
stretch and bond angles to bend. bond stretching and bending
• Protons in hydrogen-1 atoms absorb radio Infrared spectrum A plot of measured infrared
transmittance against wavenumber.
waves, which causes changes in proton spin.
• In many types of spectroscopy, radiation is • The amount of light absorbed by the molecule
(absorbance) is plotted as a function of wavelength.
passed from a source through a sample that At most wavelengths the amount of radiation
may or may not absorb certain wavelengths of detected by the detector is equal to that emitted by
the source—that is, the molecule does not absorb
the radiation. radiation.
• At a wavelength (frequency) that corresponds to the
• The wavelength (and thus frequency and
energy necessary for a molecular change, the
energy) is systematically changed, and a radiation emitted by the source is absorbed by the
detector measures any transmitted radiation. molecule.
Infrared radiation
• Infrared radiation causes certain bonds, especially polar covalent bonds, to
vibrate and undergo stretching and bending .
• Most organic molecules have bonds and functional groups that absorb
infrared radiation.
• This provides information about which functional groups are present and
can also give information about bond strength
• This is the basis of infrared spectroscopy.
• The frequencies that are absorbed depend on the strength of the bonds in
the molecule and the masses of the atoms at each end.
• The fraction of energy absorbed (the absorbance) depends on the change
in dipole moment as the bond vibrates.
• Bonds to electronegative atoms such as oxygen, which are found in ↑ Stretching and bending
alcohols (–O–H) and carbonyl compounds (>C=O), show very strong vibrations resulting from the
absorption of infrared
absorptions. radiation
Infrared spectrum
• By analysing this spectrum, we can determine details of a compound’s chemical structure.
• In particular, the spectrum of an organic compound can allow us to identify the functional groups it contains.
Each functional group has a characteristic absorption frequency or range
Infrared spectrum
of frequencies as shown in the table and can also be found in the IB
Chemistry data booklet.
Key features of
infra-red spectroscopy
Features Explanation
Uses for Identification of the:
infrared spectra • functional groups present in an organic molecule
• molecule itself (every molecule has a unique infrared spectrum).
Transmittance Ratio of the intensity of exiting light to the intensity of incident light is expressed as a percentage.
• 100% transmittance corresponds to no absorption
• 0% transmittance corresponds to total absorption
• High absorption appears as a dip in the spectrum
Wavenumber • This is equal to the number of wavelengths per centimetre and the reciprocal centimetre, cm−1
• Larger wavenumbers correspond to higher frequencies and energies
Absorption Absorption bands below 1500 cm−1 correspond to vibrations of the entire molecule or part of the
bands molecule.
This is the fingerprint region which acts as a unique identifier for a molecule.
The infrared
spectrum of
ethanol
• The horizontal scale is the wavenumber of the
infrared radiation.
• The vertical axis represents the transmittance—the
percentage of infrared radiation that passes through
the sample.
General approach to analysing infrared spectra: The infrared spectrum of ethanol shows the stretching vibrations of
• Examine the spectrum from left to right, starting at
the O−H and C−O bonds.
4000 cm−1.
• Note which are the strongest absorptions and Absorption Information
attempt to match them to Table 26 in the data band
booklet.
O−H bond vibration occurs at 3350 cm−1
• Note the absence of peaks in important areas.
• Do not attempt to match all the peaks, especially O−H bond absorption is broad (wide) because of hydrogen bonding
in the fingerprint region. C−O bond vibration occurs at 1050 cm−1
Go to pages 3 – 10 in spectroscopy booklet.
INFRA RED SPECTROSCOPY
CONTENTS
• Prior knowledge
• Origins of infra red spectra
• Vibrations of bonds in molecules
• The Infra Red spectrophotometer
• Uses of IR
• Interpretation of IR spectra
• Characteristic absorption frequencies
• Check list
INFRA RED SPECTROSCOPY
Different covalent bonds have different strengths due to the masses of different atoms at either
end of the bond.
As a result, the bonds vibrate at different frequencies
The frequency of vibration can be found by detecting when the molecules absorb electro-magnetic
radiation.
Various types of vibration are possible.
INFRA RED SPECTROSCOPY
Different covalent bonds have different strengths due to the masses of different atoms at either end of
the bond.
As a result, the bonds vibrate at different frequencies
The frequency of vibration can be found by detecting when the molecules absorb electro-magnetic
radiation.
Various types of vibration are possible.
Examples include... STRETCHING and BENDING
SYMMETRIC BENDING ASYMMETRIC
STRETCHING STRETCH
BENDING AND STRETCHING IN WATER MOLECULES
SYMMETRIC STRETCHING
BENDING AND STRETCHING IN WATER MOLECULES
ASYMMETRIC STRETCHING
BENDING AND STRETCHING IN WATER MOLECULES
BENDING
The Infra-red Spectrophotometer
• a beam of infra red radiation is passed through the sample
• a similar beam is passed through the reference cell
• the frequency of radiation is varied
• bonds vibrating with a similar frequency absorb the radiation
• the amount of radiation absorbed by the sample is compared with the reference
• the results are collected, stored and plotted
The Infra-red Spectrophotometer
A bond will absorb radiation of a frequency similar to its vibration(s)
normal vibration vibration having absorbed energy
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.
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 different vibrations taking
place in each molecule.
INFRA RED SPECTRA - INTERPRETATION
Infra-red spectra are complex due to the many different vibrations taking
place 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.
INFRA RED SPECTRA - INTERPRETATION
Infra-red spectra are complex due to the many different vibrations taking
place 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.
The technique is useful when used in conjunction with other methods -
nuclear magnetic resonance spectroscopy and mass spectroscopy.
INFRA RED SPECTRA - INTERPRETATION
Infra-red spectra are complex due to the many different vibrations taking
place 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.
The technique is useful when used in conjunction with other methods -
nuclear magnetic resonance 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 CN C-Cl
O-H C=O C-O
C-H Aromatic C-C
C=C C-C alkanes
Bond Class of compound Range / cm-1 Intensity
C-H Alkane 2965 - 2850 strong
C-C Alkane 1200 - 700 weak
CHARACTERISTIC C=C Alkene 1680 - 1620 variable
ABSORPTION C=O Ketone 1725 - 1705 strong
FREQUENCIES C=O 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
CN Nitrile 2260 - 2240 medium
C-X Chloride 800 - 600 Strong
Bromide 600 - 500 Strong
Iodide 500 (approx) Strong
