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OCR A Level Chemistry Your notes

6.9 Analytical Techniques

Contents
6.9.1 Thin Layer Chromatography, TLC
6.9.2 Gas Chromatography, GC
6.9.3 Qualitative Analysis
6.9.4 Carbon-13 NMR
6.9.5 Proton NMR
6.9.6 Combined Techniques

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6.9.1 Thin Layer Chromatography, TLC

Your notes
Thin-Layer Chromatography Practical
Thin-layer chromatography (TLC) is a technique used to analyse small samples via separation
For example, we could separate a dye out to determine the mixture of dyes in a forensic sample
There are 2 phases involved in TLC:
Stationary phase
This phase is commonly thin metal sheet coated in alumina (Al2O3) or silica (SiO2)
The solute molecules adsorb onto the surface
Depending on the strength of interactions with the stationary phase, the separated
components will travel particular distances through the plate
The more they interact with the stationary phase, the more they will 'stick' to it
Mobile phase
Flows over the stationary phase
It is a polar or non-polar liquid (solvent) that carries components of the compound being
investigated
Polar solvents - water or alcohol
Non-polar solvents - alkanes
If the sample components are coloured, their spots are easily identifiable on the chromatogram
If the sample components are not coloured, then we can locate the spots on the chromatogram and
draw around them in pencil
To locate the spots we can use:
UV light
Ninhydrin (carcinogenic)
Iodine vapour

Conducting a TLC analysis

Step 1:
Prepare a beaker with a small quantity of solvent
Step 2:
On a TLC plate, draw a horizontal line at the bottom edge (in pencil)
This is called the baseline
Step 3:
Place a spot of pure reference compound on the left of this line, then a spot of the sample to be
analysed to the right of the baseline and allow to air dry
The reference compounds will allow identification of the mixture of compounds in the sample

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Step 4:
Place the TLC plate inside the beaker with solvent - making sure that the solvent does not cover the
spot - and place a lid to cover the beaker Your notes
The solvent will begin to travel up the plate, dissolving the compounds as it does
Step 5:
As solvent reaches the top, remove the plate and draw another pencil line where the solvent has
reached, indicating the solvent front
The sample’s components will have separated and travelled up towards this solvent front

A dot of the sample is placed on the baseline and allowed to separate as the mobile phase flows through
the stationary phase; The reference compound/s will also move with the solvent

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TLC & Rf Values

Your notes
Rf values
A TLC plate can be used to calculate Rf values for compounds
Distance travelled by component
Rf =
Distance travelled by solvent
These values can be used alongside other analytical data to deduce composition of mixtures

Rf values can be calculated by taking 2 measurements from the TLC plate

Examiner Tip
The baseline on a TLC plate must be drawn in pencil. Any other medium would interact with the sample
component and solvents used in the analysis process.

The less polar components travel further up the TLC plate

Their Rf values are higher than those closer to the baseline
They are more soluble in the mobile phase and get carried forwards with the solvent
More polar components do not travel far up the plate

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They are more attracted to the polar stationary phase

The extent of separating molecules in the investigated sample depends on the solubility in the mobile
and stationary phases Your notes
Knowing the Rf values, of compounds being analysed, helps to compare the polarity of various
molecules

Worked example
A mixture of amino acids is analysed by thin layer chromatography (TLC). The TLC plate produced is
shown below. Identify the amino acids in the sample using the table of values for Rf.

Answers:
Blue spot Rf value = 2.82 ÷ 4.63= 0.61 = Leucine
Green spot Rf value = 2.45 ÷ 4.63= 0.536 = Isoleucine
Red spot Rf value = 2.04 ÷ 4.63= 0.44 = Valine

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6.9.2 Gas Chromatography, GC

Your notes
Interpreting Gas Chromatograms
Gas-Liquid Chromatography (GLC) is used for analysing:
Gases
Volatile liquids
Solids in their vapour form
The stationary phase:
This method uses a long coiled column for the stationary phase
Normally a non-volatile liquid is the stationary phase in GLC
The Mobile phase
An inert carrier gas (e.g. helium, nitrogen) moves the sample molecules through the stationary
phase
The sample is injected into the column through a self-sealing disc and the vapour formed is carried
through the stationary phase using the inert-gas mobile phase

Retention times
Once sample molecules reach the detector, their retention times are recorded
This is the time taken for a component to travel through the column
It depends upon the attraction between the solute and the stationary and mobile phases as well as
the volatility and nature of the solute
The retention times are recorded on a chromatogram where each peak represents a volatile
compound in the analysed sample
The relative sizes (i.e. areas) of the peaks are related to how much of each compound is present in
the mixture
Retention times are then compared with data book values to identify unknown molecules

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Your notes

A gas chromatogram of a volatile sample compound has six peaks. Depending on each molecule’s
interaction with the stationary phase, each peak has its own retention time

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Worked example
Your notes
Analysis of a compound by GLC shows the presence of four components, A, B, C and D.

i) Which compound is present in the greatest quantity?

ii) Which compounds were present in equal amounts?
iii) Which compound had the strongest interaction with the stationary phase?

Answers:
i) D (the larger the relative size of the peak, the greater the quantity of that substance present)
ii) B and C (the peak sizes are equal)
iii) D (the larger the retention time, the greater the interaction of that component with the stationary
phase)

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6.9.3 Qualitative Analysis

Your notes
Testing for Alkenes & Haloalkanes
Testing for an Alkene
Halogens can be used to test if a molecule is unsaturated (i.e. contains a double bond)
Br2(aq) is an orange-yellow solution, called bromine water
The unknown compound is shaken with the bromine water
If the compound is unsaturated, an addition reaction will take place and the coloured solution will
decolourise

The bromine water test is the standard test for unsaturation in alkenes

Testing for a haloalkane

The haloalkane must first be warmed with sodium hydroxide in a mixture of ethanol and water
The haloalkane will undergo nucleophilic substitution releasing the halide ion into solution, which can
then be tested
The released halide ion is tested for using the silver nitrate test:

Acidify the sample with dilute nitric acid (HNO3) followed by the addition of silver nitrate solution,
AgNO3
The acidification is done to remove carbonate ions that might give a false positive result

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If a halide is present it forms a silver halide precipitate:

Ag+ (aq) + X– (aq) → AgX (s)
Your notes
Depending on the halide present, a different coloured precipitate is formed, allowing for
identification of the halide ion
Silver chloride is white, silver bromide is cream and silver iodide is yellow

Each silver halide produces a precipitate of a different colour

Examiner Tip
The acidification step in the halide ion test must be done with nitric acid rather than hydrochloric acid,
as HCl contains chloride ions which would interfere with the results.

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Testing for Carbonyls & Alcohols

Testing for a carbonyl Your notes
2,4-dinitrophenylhydrazine or Brady's reagent
2,4-dinitrophenylhydrazine (2,4-DNP or 2,4-DNPH) is used to test for the presence of a carbonyl
group, C=O
2,4-DNP is usually dissolved in methanol and sulfuric acid
It is a pale orange solution
A few drops of the unknown sample are added to 5.0 cm3 of 2,4-DNP and it left to stand
A few drops of sulfuric acid are then added to the mixture
The formation of an orange / yellow precipitate of 2,4-dinitrophenylhydrazone confirms the
presence of an aldehyde or ketone

Examiner Tip
It is more common to use other chemical tests to more specifically check for the presence of an
aldehyde or a ketone because:
1. Brady's reagent / 2,4-DNP only confirms the presence of a carbonyl group, it does not distinguish
between an aldehyde and a ketone
2. Friction or sudden impacts can cause solid 2,4-DNP to explode

Testing for an Aldehyde

Tollens’ reagent
Tollens' reagent is an aqueous alkaline solution of silver nitrate in excess ammonia solution
Tollens' reagent is also called ammoniacal silver nitrate solution
When warmed with an aldehyde, the aldehyde is oxidised to a carboxylic acid and the Ag+ ions are
reduced to Ag atoms
In the alkaline conditions, the carboxylic acid will become a carboxylate ion and form a salt
The Ag atoms form a silver ‘mirror’ on the inside of the tube
Ketones cannot be oxidised and therefore give a negative test when warmed with Tollens’ reagent

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Your notes

The Ag+ ions in Tollens’ reagent are oxidising agents, oxidising the aldehyde to a carboxylic acid and
getting reduced themselves to silver atoms

Examiner Tip

Fehling’s solution can also be used to test for an aldehyde

An aldehyde cause a change from a blue solution to a orange / brick-red prcipitate
There is no visible change for a ketone

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Testing an Alcohol
Alcohols can be classified as either primary, secondary or tertiary, depending on the placement of the - Your notes
OH group
Primary and secondary alcohols can both be oxidised, but tertiary alcohols cannot
To test for the alcohol functional group, add a small amount (1 cm3) of the substance to a test tube
using a pipette
Then, add a small amount (1 cm3) of a suitable oxidising agent to the sample using a different pipette
The most commonly used oxidising agent for this test is acidified potassium dichromate solution
(K2Cr2O7, acidified with H2SO4)
Add a stopper to the test tube and shake well
Place in a hot water bath (heated to around 60 oC) for a few minutes
If a primary or secondary alcohol are present, then the colour will change from orange to green
If a tertiary alcohol is present, then nothing will happen - the solution will remain orange

Positive test results of the oxidation of a primary, secondary and tertiary alcohol

Examiner Tip
When heated with acidified potassium dichromate, an aldehyde will also cause a colour change from
orange to green

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Testing for Carboxylic Acids & Phenols

Your notes
Testing for a Carboxylic Acid
Carboxylic acids in solution have a pH of around 3, so measuring the pH is a way of testing for the
presence of the carboxylic acid functional group in an organic sample
The end of a glass rod could be dipped into the solution and then carefully dripped onto indicator
paper
Or, a pH probe could be used, which would give you an exact pH
Since carboxylic acids are acids, they will react with a carbonate solution to produce carbon dioxide
gas
1-2 cm3 of sodium carbonate (Na2CO3) or sodium hydrogen carbonate solution (NaHCO3) could be
added using a pipette
If bubbles of gas are seen, this is a good indicator that the solution is a carboxylic acid
If an exam question asks you to simply distinguish between different types of organic compound,
and the carboxylic acid is the only organic compound present which would react in this way with a
carbonate solution, then this is enough
The gas produced could then be bubbled into limewater
If the limewater turns milky or cloudy, then this proves that the gas produced was carbon dioxide

Testing for Phenols

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Bromine water can be used to test if a molecule is phenolic (i.e. contains phenol)
The unknown compound is shaken with the bromine water
If the compound contains phenol, a substitution reaction will take place and the coloured bromine Your notes
water will decolourise and then a white precipitate will form

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6.9.4 Carbon-13 NMR

Your notes
Carbon-13 NMR
Nuclear Magnetic Resonance (NMR) spectroscopy is used for analysing organic compounds
Atoms with odd mass numbers usually show signals on NMR
For example, isotopes of atoms
Many of the carbon atoms on organic molecules are carbon-12
A small quantity of organic molecules will contain the isotope carbon-13 atoms
These will show signals on a 13C NMR
In 13C NMR, the magnetic field strengths of carbon-13 atoms in organic compounds are measured and
recorded on a spectrum
Just as in 1H NMR, all samples are measured against a reference compound – Tetramethylsilane (TMS)
On a 13C NMR spectrum, non-equivalent carbon atoms appear as peaks with different chemical shifts

Chemical shift values (relative to the TMS) for 13C NMR analysis table

Bond Groups Chemical shift range, δ / ppm

C–C alkyl 0 - 50

C–Cl or C–Br haloalkanes 20 - 50

C–N amines 30 - 70

C–O alcohols, ethers or esters 50 - 90

aryl C=C 110 - 160

C=C

C=O aldehydes, ketones, esters or carboxylic acids 160 - 220

Features of a 13C NMR spectrum

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13C NMR spectrum displays sharp single signals

There are no complicated splitting patterns like 1H NMR spectra
Your notes
The height of each signal is not proportional to the number of carbon atoms present in a single
molecular environment
Carbon atoms in different chemical environments will give resonances at different chemical shifts in a
13C spectrum
As with 1H NMR, tetramethylsilane is used as the standard reference point for 13C at 0 ppm

Identifying 13C molecular environments

On an organic molecule, the carbon-13 environments can be identified in a similar way to the proton
environments in 1H NMR
For example propanone
There are 2 molecular environments
2 signals will be present on its 13C NMR spectrum

There are 2 molecular environments in propanone

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Your notes

The 13C NMR of propanone showing 2 signals for the 2 molecular environments

Examiner Tip
Counting the number of 13C resonances should be the first step in analysing a spectrum. For example,
it is possible to differentiate the three isomers of dihydroxybenzene quickly be considering the
symmetry of the molecules and therefore the number of resonances expected in their spectra.

Worked example
How many chemical environments and therefore number of peaks / resonances would be in a 13C
spectra of 1,3-dihydroxybenzene?

Answer:
4 chemical environments and therefore four peaks / resonances on the spectra

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Your notes

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6.9.5 Proton NMR

Your notes
Low & High Resolution Proton NMR
Features of a 1H NMR spectrum
An NMR spectrum shows the intensity of each peak against its chemical shift
The area under each peak gives information about the number of protons in a particular environment
The area under each peak shows the intensity / absorption from protons
A single sharp peak is seen to the far right of the spectrum
This is the reference peak from TMS
By definition the chemical shift is at 0 ppm

A low resolution 1H NMR for ethanol showing the key features of a spectrum

Molecular environments
1H nuclei that have different neighbouring atoms (said to have different chemical environments)
absorb at slightly different field strengths
The difference environments are said to cause a chemical shift away from TMS
Ethanol has the structural formula CH3CH2OH
There are 3 chemical environments: -CH3, -CH2 and -OH

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The hydrogen atoms in these environments will appear at 3 different chemical shifts
Different types of protons are given their own range of chemical shifts
Your notes
Worked example
How many different 1H chemical environments occur in 2-methylpropane?

Answer:
Two different 1H chemical environments occur in 2-methylpropane
The three methyl groups are in the same 1H environment
The lone hydrogen is in its own 1H environment

Chemical shift values for 1H molecular environments table

Environment of proton Chemical shift range, δ / ppm

R–CH 0.5 - 2.0

2.0 - 3.0

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Your notes

N–CH
O–CH
Cl–CH 3.0 - 4.2
Br–CH

4.5 - 6.0

6.2 - 8.0

9.0 - 10.0

10.0 - 12.0

R–OH
0.5 - 12.0
R–NH

Protons in the same chemical environment are chemically equivalent

1,2-dichloroethane, Cl-CH2-CH2-Cl has one chemical environment as these four hydrogens are all
exactly equivalent
Each individual peak on a 1H NMR spectrum relates to protons in the same environment
Therefore, 1,2-dichloroethane would produce one single peak on the NMR spectrum as the
protons are in the same environment

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Your notes

Low resolution 1H NMR

Peaks on a low resolution NMR spectrum refer to molecular environments of an organic compound
Ethanol has the molecular formula CH3CH2OH
This molecule as 3 separate proton environments: -CH3, -CH2, -OH
So 3 peaks would be seen on its spectrum at 1.2 ppm (-CH3), 3.7 ppm (-CH2) and 5.4 ppm (-OH)
The strengths of the absorptions are proportional to the number of equivalent 1H atoms and are
proportional to the area underneath each absorption peak
Hence, the areas of absorptions of -CH3, -CH2, -OH are in the ratio of 3:2:1 respectively

A low resolution NMR spectrum of ethanol showing 3 peaks for the 3 molecular environments

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High resolution 1H NMR

More structural details can be deduced using high resolution NMR Your notes
The peaks observed on a high resolution NMR may sometimes have smaller peaks clustered together
The splitting pattern of each peak is determined by the number of protons in neighbouring
environments

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Spin-Spin Splitting Patterns

Your notes
Spin-Spin Splitting
A high resolution 1H NMR spectrum can show you the structure of the molecule but also the peaks can
be split into sub-peaks or splitting patterns
These are caused by a proton's spin interacting with the spin states of nearby protons that are in
different environments
This can provide information about the number of protons bonded to adjacent carbon atoms
The splitting of a main peak into sub-peaks is called spin-spin splitting or spin-spin coupling

High resolution 1H NMR spectrum of ethanol showing the splitting patterns of each of the 3 peaks. Using
the n+1, it is possible to interpret the splitting pattern

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Examiner Tip
Your notes
It is very rare that the spin-spin splitting of equivalent protons is covered in teaching because it is
so rarely asked in exams
Equivalent protons do not cause spin-spin splitting
The simplest example of this is benzene
In benzene, all of the protons are equivalent
This means that they are seen as one singlet in the high resolution 1H NMR spectrum of
benzene

The n+1 rule

The number of sub-peaks is one greater than the number of adjacent protons causing the splitting
For a proton with n protons attached to an adjacent carbon atom, the number of sub-peaks in a
splitting pattern = n+1
When analysing spin-spin splitting, it shows you the number of hydrogen atoms on the adjacent
carbon atom
These are the splitting patterns that you need to be able to recognise from a 1H spectra:

1H NMR peak splitting patterns table

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Your notes

Splitting patterns must occur in pairs, because each protons splits the signal of the other
There are some common splitting pairs you will see in a spectrum however you don't need to learn
these but can be worked out using the n+1 rule
You will quickly come to recognise the triplet / quartet combination for a CH3CH2 because it is so
common

Common pair of splitting patterns

A quartet and a triplet in the same spectrum usually indicate an ethyl group, CH3CH2-
The signal from the CH3 protons is split as a triplet by having two neighbours
The signal from the CH2 protons is split as a quartet by having three neighbours
Here are some more common pairs of splitting patterns

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Your notes

Common pairs of splitting patterns

1H NMR spectrum of propane

The CH2 signal in propane (blue) is observed as a heptet because it has six neighbouring equivalent H
atoms (n+1 rule), three either side in two equivalent CH3 groups
The CH3 groups (red) produce identical triplets by coupling with the CH2 group

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Worked example
Your notes
For the compound (CH3)2CHOH predict the following:
i) the number of peaks
ii) the type of proton and chemical shift (using the Data sheet)
iii) the relative peak areas
iv) the splitting pattern

Answers:
i) 3 peaks
ii) (CH3)2CHOH at 0.7 - 1.2 ppm, (CH3)2CHOH at 3.1 - 3.9 ppm, (CH3)2CHOH at 0.5 - 5.5 ppm
iii) Ratio 6 : 1 : 1
iv) (CH3)2CHOH split into a doublet (1+1=2), (CH3)2CHOH split into a heptet (6+1=7)

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Tetramethylsilane as a Standard
Your notes
Tetramethylsilane
The horizontal scale on an NMR spectrum represents chemical shift (δ)
Chemical shift is measured in parts per million (ppm) of the radio frequency needed for resonance
compared to a reference chemical called tetramethylsilane, abbreviated to TMS

The displayed formula of tetramethylsilane

TMS is used universally as the reference compound for NMR as its methyl groups are particularly well
shielded and so it produces a strong, single peak at the far right of an NMR spectrum
The signal from the hydrogen atoms in TMS is defined as having a chemical shift of 0 ppm

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Your notes

The NMR reference peak for TMS

Hydroxyl and amino protons
Organic compounds often contain protons from part of a functional group rather than being bonded
to a carbon, examples include:
Alcohols, ROH
Carboxylic acids, RCOOH
Phenols, ArOH
Amines, RNH2
Amides, RCONH2
Amino acids, H2NCHRCOOH
These hydroxyl, OH, protons and amino, NH, protons can be involved in hydrogen bonding which
causes their peaks to be broader than normal and they can appear at almost any chemical shift
The broadening of the peak means that they are not usually involved in spin-spin coupling and
therefore appear as singlets
Deuterated solvents
Deuterated solvents such as D2O (heavy water) and CDCl3 can be used to identify OH and NH protons
This is achieved by:
Performing a standard proton NMR on the sample compound
A small amount of the deuterated solvent is added to the sample compound and mixed
A second proton NMR is then performed
Deuterium atoms from the solvent replace the OH and NH protons in the sample, e.g for ethanol
C2H5OH + CDCl3 ⇌ C2H5OD + CHCl3

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This means that the second proton NMR will still have the peaks for the CH3 and CH2 protons of ethanol
but will not have the OH peak as that proton has been exchanged
Your notes

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6.9.6 Combined Techniques

Your notes
Deducing Organic Structures
Organic chemists use a variety of techniques to determine an organic structure
In real laboratory practice, certain pieces of information might already be known as target
molecules are often tested once they are produced to check that the reaction has gone as
planned
The typical sequence using the common analytical techniques would be:
1. Elemental analysis - to determine the empirical formula
2. Mass spectrometry - to determine the molecular mass, and consequently the molecular formula,
as well as fragments of the molecule
3. Infrared spectrometry - to primarily identify functional groups but also identify types of bond, e.g.
C-C, C=C
4. NMR spectrometry - to determine the number of carbon / hydrogen atoms and their environments
Each technique provides valuable information that can be used to propose a structure, although some
techniques provide more information than others
Elemental analysis is sometimes skipped as the combination of mass spectrometry and NMR can
suggest the molecular formula without the need for elemental analysis

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Worked example
Your notes
An unknown compound, X, of molecular formula, C4H8O, has the following MS, IR and 1H NMR spectra.

MS of X

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IR spectrum of X

Your notes

1H NMR spectrum of X

Deduce the structure of X using the information given and any other additional information in the Data
booklet. For each spectrum assign as much spectroscopic information as possible.

Answer
Mass Spectrum
The molecular ion peak is at m/z = 72, which corresponds to the relative molecular mass of
C 4H 8 O
Mr = (12 × 4) + (8 × 1) +(16) = 72
The large peak at m/z = 43 could correspond to CH3CH2CH2+ or CH3CO+ indicating the loss of
CH4O or C2H5 from X, that is (Mr - 43)
The peak at m/z = 29 could correspond to CH3CH2+ indicating the loss of C2H3O from X, that
is (Mr - 29)
IR Spectrum

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There is a strong absorption in the range 1700-1750 cm-1 which corresponds to C=O, based
on Section 26 of the Data book
This suggests an aldehyde or ketone is present (it cannot be an ester or carboxylic acid as only Your notes
one oxygen is in the formula)
1H NMR Spectrum

The 1H NMR spectrum shows three protons environments

The peak around chemical shift 1.0 ppm could correspond to a proton on the end of a chain, -
CH3
The peaks around chemical shift 2.2 - 2.7 ppm could correspond to a proton next to a carbonyl
group RCH2CO-
The peak splitting is a quartet, singlet and triplet
A quartet and triplet in the same spectrum usually corresponds to an ethyl group, CH3CH2,
following the n+1 rule
The singlet indicates an isolated proton environment
Putting the information together the structure of X is

The structure of X is butanone

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