ORGANIC ANALYSIS
3.3.6
TEST TUBE REACTIONS
FUNC. GROUP REAGENT RESULT NOTES
Alkene Bromine water Orange →colourless Add solution then shake.
Haloalkane NaOH, warm, HNO3, AgNO3 Precipitates of AgX
AgCl - white
AgBr - cream
AgI - yellow
Alcohol K2Cr2O7 (VI) and H2SO4 1ry - orange →green The green to orange is the
2ry - orange →green orange dichromate (VI) being
3ry - orange remains (no reac.) reduced to green chromium (III)
Cr3+. same result for 1ry and 2ry
so need further test.
Aldehyde Warm with: Fehling’s - blue →red precipitate To test between aldehydes and
Fehling's reagent Tollen’s - silver mirror forms (Ag 0) ketones, ketones do not get
Tollens’ solution oxidised so nothing happens.
Carboxylic acid NaHCO3 (carbonates) Fizzes and produces CO2 which is bubbles
through limewater →cloudy
MASS SPECTROMETRY slide 9
● It is the main method for finding the relative molecular mass of organic
compounds.
● The compound enters the mass spectrometer in solution.
● It is ionised and the positive ions are accelerated through the instrument as a
beam of ionised molecules.
● These then fly through the instrument towards a detector.
● Their times of flight are measured.
● These depend on the mass to charge ratio m/z of the ion.
● The output is then presented as a graph of relative abundance (vertical axis)
against mass/charge ratio (horizontal axis).
● However, since the charge on the ions is normally +1, the horizontal axis is
effectively relative mass.
MASS SPECTRA AND FRAGMENTATION
Molecular peak = highest peak furthest right (the molecular mass)
Fragmentation = When many of the ions break up because some of their bonds
break as they are ionised, so there are other ions of smaller molecular mass. Each
of these fragment ions produces a line in the mass spectrum. These can provide
information that will help to deduce the structure of the compound. They also act
as a 'fingerprint' to help identify it.
HIGH RESOLUTION MASS SPECTROMETRY
EXTREMELY ACCURATE MASSES
Mass spectra often show masses to the nearest whole number only. However, high
resolution mass spectrometers can measure masses to three or four decimal places.
This method allows us to work out the molecular formula of the parent ion.
lt makes use of the fact that isotopes of atoms do not have exactly whole number
atomic masses (except for carbon-12 which is exactly twelve by definition).
16
O =15.99491 and 1H = 1.007829 etc.
Adding up the accurate relative atomic masses will give the accurate molecular
mass and can deduce the molecular formula.
BOND VIBRATIONS
A pair of atoms joined by a chemical bond is always vibrating.
Stronger bonds vibrate faster (at higher frequency)
Heavier atoms make the bond vibrate more slowly (at lower frequency).
Every bond has its own unique natural frequency that is in the infrared region of the
electromagnetic spectrum.
Symmetric stretch Asymmetric stretch Bending
HOW INFRARED SPECTROMETRY WORKS
1. A beam of IR radiation is passed through a sample of a chemical.
2. The IR is absorbed by the covalent bonds in the molecules.
⤷ Bonds between different atoms absorb different frequencies of IR
radiation.
3. This increases the bond’s vibrational energy.
4. Any particular bond can only absorb radiation that has the same frequency as
the natural frequency of the bond.
5. Therefore, the radiation that emerges from the sample will be missing the
frequencies that correspond to the bonds in the sample.
6. The instrument plots a graph of the intensity of the radiation emerging from
the sample, called the transmittance, against the frequency of radiation.
7. The frequency is expressed as a wavenumber, measured in cm-1.
(wavelength = 1/frequency).
FINGERPRINTING
Below 1500 cm-1.
○ It usually has many peaks caused by complex vibrations of the whole molecule.
○ This shape is unique for any particular substance.
○ It can be used to identify the specific chemical after you’ve found the functional
group.
○ A computer database checks the fingerprint region of the unknown compound’s IR
spectrum against known compounds.
IDENTIFYING IMPURITIES
Can be used to test purity of a compound by comparing the spectrum to the pure
compound spectrum.
Extra peaks show impurities.
THE INFRARED SPECTRUM
The dips in the graph (peaks) BOND FOUND IN WAVENUMBER RANGE
represent particular bonds. N-H Amines 3300-3500
O-H (alcohols) Alcohols 3230-3550
● Below 1500 cm-1 is
fingerprinting. C-H Most organic molecules 2850-3300
● Above 1500 cm-1 is the
O-H (acids) Carboxylic acids 2500-3000
functional group signals:
CN Nitriles 2220-2260
The C=O bond is in a lot of
C=O Aldehydes , ketones, carboxylic acids, esters 1680-1750
functional groups, so look for the
other peaks. C=C Alkenes 1620-1680
C-O Alcohols, carboxylic acids 1000-1300
C-C Most organic molecules 750-1100
C=C
1620-1680 cm-1
O-H (alcohol) O-H (acid)
3230-3550 cm-1 2500-3000
cm-1
C=O
1680-1750 cm-1
© [Link] AS 1087 12-Jul-15
ALKENES (C=C)
C=C
C=H
KETONE (C=O)
C=O
C-H
short
chain
ALDEHYDE (C=O)
C=O
C-H longer
chain than
ketone
ESTERS (C=O, C-O)
C=O
C-O
C-H
CARBOXYLIC ACIDS (O-H and C=O)
O-H and C-H signals overlap.
O-H
C-H
C=O
ALCOHOL (O-H)
O-H
C-H
INFRARED ABSORPTION AND GLOBAL WARMING
● The sun emits electromagnetic radiation which reaches the earth and is
absorbed.
● The earth re-emits some of the EM radiation as infrared radiation (heat).
● IR radiation is absorbed by bonds in greenhouse gases (CO2, CH4, H2O)
● Some is re-emitted back to earth.
● The greenhouse effect is increasing due to human activities, this leads to
more IR being absorbed and global warming
