6.3.2 Spectroscopy PhysicsAndMathsTutor.

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Spectroscopy
1(a). An organic compound I is analysed, using a combination of techniques. The analytical data is
shown below.

Elemental analysis by mass

C, 56.69%; H, 7.09%; N, 11.02%; O, 25.20%

Mass spectrum
Molecular ion peak at m/z = 127.0

IR spectrum

Proton NMR spectrum

* Determine the structure of compound I, showing all your reasoning.

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(b). Explain the use of two deuterated compounds in NMR spectroscopy.

[2]
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2. Compounds B and C, shown below, are unsaturated hydrocarbons containing nine carbon
atoms.

An organic chemist is investigating compound D for possible use as a medicine.

The chemist proposes a synthesis of compound D from compound C.

i. Predict the number of peaks in the 13C NMR spectra of compounds C and D.

Compound C Compound D

Number of peaks .................. ..................

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ii. The chemist develops a three-stage synthesis of compound D from compound C.

Complete the flowchart.

Show structures for organic compounds.

[5]
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3. This question is about organic chemistry.

This part is about amines.

i. The table shows the structures and boiling points of three amines, which are structural
isomers of C3H9N.

Amine CH3CH2CH2NH2 (CH3)2CHNH2 (CH3)3N

Skeletal formula

Boiling point / °C 48–49 °C 33–34 °C 3–4 °C

Explain the difference in the boiling points of the three amines.

[4]
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ii. Amine A is a liquid at room temperature and pressure.

When vaporised, 0.202 g of the amine produces 72.0 cm3 of gas at 1.00 × 105 Pa and
100 °C. The 13C NMR spectrum of amine A has 3 peaks.

Determine the molecular formula of A and suggest a possible structure for amine A.

Molecular formula of A ...............................................................

Structure of A
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4(a). This question is about esters.

The structure of ester A is shown below.

i. What is the systematic name of ester A?

[1]
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ii. In the boxes, draw the organic products for the reactions of the functional groups in ester
A shown below.
Each reaction forms two organic products.

[5]

iii. Name the type of reactions of ester A shown in (ii).

[1]

(b). The protons in ester A are in four different environments, labelled 1– 4 on the structure below.

Complete the table to predict the proton NMR spectrum of ester A.

Proton environment Chemical shift Splitting pattern

[4]
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(c). Compound B is a structural isomer of ester A.

• Compound B reacts with aqueous sodium carbonate.

• The 13C NMR spectrum of B has 4 peaks.

Draw a possible structure for compound B.

[1]

(d). A polyester is formed from 200 molecules of 4-hydroxybenzoic acid.

What is the relative molecular mass, Mr, of the polyester?

Mr = ................................................. g mol−1 [2]

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(e). * A student intends to synthesise ester C.

i. Plan a two-stage synthesis to prepare 12.75 g of ester C starting from 2-methylpropanal,

(CH3)2CHCHO. Assume the overall percentage yield of ester C from 2-methylpropanal is
40%.

In your answer include the mass of 2-methylpropanal required, reagents, conditions and
equations where appropriate.

Purification details are not required.

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ii. The mass spectrum of ester C is shown below.

Suggest possible structures for the species responsible for peaks Y and Z in the mass
spectrum.

Y Z
[2]
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5. * Analysis of an unknown organic compound produced the following results.

Elemental analysis by mass

C: 73.17%; H: 7.32%; O: 19.51%

Mass spectrum
Molecular ion peak at m / z = 164.0

The numbers by the peaks are the relative peak areas.

Use the results to suggest one possible structure for the unknown compound.

Show all your reasoning.

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[6]

6. A scientist is researching compounds that might be suitable as fuel additives.

One of the compounds gives the analytical results below.

Elemental analysis by mass:

C: 54.54%; H: 9.10%; O: 36.36%

Mass spectrum:
Molecular ion peak at m/z = 132.0
1H NMR spectrum in D2O

The numbers by the peaks are the relative peak areas.

When the spectrum is run without D2O, there are two additional peaks with the same relative
peak areas at 11.0 ppm and 3.6 ppm.
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Use the information provided to suggest a structure for the compound.

Show all your reasoning. [6]

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7. A cosmetic product containing four esters, J, K, L and M, is analysed by gas chromatography

and mass spectrometry. The results are shown below.

Gas chromatogram

The numbers by the peaks are the relative molar proportions of the compounds in the mixture.

Mass spectrometry

ester m/z of molecular ion peak

J 152
K 166
L 180
M 180

i. The concentration of ester K in the cosmetic product is 9.13 × 10−2 g dm−3.

Using the results, calculate the concentration, in mol dm−3, of ester M in the cosmetic
product.

Give your answer to two significant figures.

concentration of ester M
mol dm−3 [2]
=
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ii. A general structure for esters J, L and M is shown below.

Where ‘R’ is an alkyl group.

Use the mass spectrometry results to deduce possible structures for esters J, L and M.

[3]

8. This question is about aromatic compounds.

Phenol undergoes nitration more readily than benzene.

i. A student carries out the nitration of phenol with dilute nitric acid to produce 2-
nitrophenol and 4-nitrophenol.

A small amount of 3-nitrophenol is also produced.

The student thought that 13C NMR spectroscopy could be used to distinguish between
these three nitrophenols.

Explain whether the student is correct.

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ii. Explain why phenol is nitrated more readily than benzene.

[3]
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9(a). A chemist analyses a naturally occurring aromatic compound.

The percentage composition and mass spectrum of the compound are shown below.
Percentage composition by mass: C, 70.58%; H, 5.92%; O, 23.50%.
Mass spectrum

Determine the molecular formula of the compound.

Show your working.
molecular formula = ......................................... [3]

(b). Qualitative tests are carried out on the aromatic compound. The results are shown below.

Test Acidity Na2CO3(aq) 2,4-DNP Tollens’ reagent

No observable No observable
Observation pH = 5 Orange precipitate
change change

Determine the functional groups in the compound. Explain your reasoning.

Functional
groups

Explanation

[3]
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(c). The carbon-13 NMR spectrum of the compound is shown below.

Using the spectrum and the results from (a) and (b), determine the structure of the compound.
Explain your reasoning.

[3]
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10. Fruit juice contains a mixture of organic acids.

*Acid C is an aliphatic organic acid present in fruit juice.

Information about acid C is shown below:

• 1.21 × 10−2 mol C has a mass of 2.323 g.

• The molecular formula of C is CxHyO7.
• 1 mol of acid C requires 3 mol NaOH for neutralisation.
• Acid C contains a hydroxyl group but produces no colour change with hot acidified
dichromate(VI).
• The 13C NMR spectrum of C has four peaks.

Analyse this information to determine the structure of acid C.

Show all your reasoning.

[6]
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11(a). A student was provided with five compounds: an aldehyde, a ketone, a carboxylic acid and two
esters. The student decides to identify the type of compound by carrying out some chemical
tests.

Suggest chemical tests to identify the carboxylic acid and aldehyde.

For each test, include essential reagent(s), observation(s) and a balanced equation.

In your equations, use ‘R’ for the alkyl group.

i. Test for carboxylic acid.

Reagent(s)
.............................................................................................................................................

Observation(s)
.......................................................................................................................................

Equation

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ii. Test for aldehyde.

Reagent(s)
.............................................................................................................................................

Observation(s)
.......................................................................................................................................

Equation

[2]

(b). Suggest a chemical test to distinguish the ketone from the two esters.

Reagent(s)
...................................................................................................................................................

Observation(s)
............................................................................................................................................

[1]
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(c). The student wants to confirm that the other two compounds are esters. Unfortunately there is no
direct test for an ester group.

The esters are CH3COOC(CH3)3 and (CH3)3CCOOCH3.

The student plans the following:

• hydrolyse the two esters using aqueous sodium hydroxide.

• separate the hydrolysis products.
• carry out tests on the hydrolysis products.

i. Write an equation for the hydrolysis of one of the two esters with aqueous sodium
hydroxide.

Show the structures for the organic compounds.

[2]

ii. Suggest a chemical test on the hydrolysis products that would allow the two esters to be
identified.

Write an equation for one reaction that takes place.

Show the structures for the organic compounds.

Reagent(s)
.............................................................................................................................................

Observation(s)
.......................................................................................................................................

Equation

[2]
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iii. The student thought that NMR spectroscopy could be used to identify the two esters
without the need to carry out chemical tests.

The esters are CH3COOC(CH3)3 and (CH3)3CCOOCH3.

Explain whether the student is correct for 13C and 1H NMR spectroscopy. Your answer
should also clearly state any differences between the spectra of the two esters.

[3]

(d). The ketone and aldehyde provided to the student both contain five carbon atoms.

The 1H NMR spectrum of the aldehyde contains two singlet peaks only:
a large peak at δ = 1.2 ppm and smaller peak at δ = 9.6 ppm.

Suggest all possible structures for the ketone and identify the aldehyde.

Show all your reasoning.

[5]
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12. *Compound J is an organic compound containing carbon, hydrogen and nitrogen only.

A chemist analyses compound J and the results are shown below:

Elemental analysis by mass:

C: 74.17%; H: 11.41%; N, 14.42%

Mass spectrum
Molecular ion peak at m/z = 97.0

Use the information provided to suggest a structure for compound J.

Show all of your reasoning.

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[6]

13(a). A chemistry teacher carries out an experiment to synthesise 2-aminopropan-1-ol,

CH3CH(NH2)CH2OH.

The teacher asks a university chemistry department to test the 2-aminopropan-1-ol using proton
NMR spectroscopy and mass spectrometry.

i. For the 1H NMR analysis, the sample was dissolved in D2O.

Complete the table to predict the 1H NMR spectrum of CH3CH(NH2)CH2OH after

dissolving in D2O.

1H NMR spectrum for CH3CH(NH2)CH2OH, dissolved in D2O

Chemical shift, δ/ ppm Relative peak area Splitting pattern

[3]

ii. The mass spectrum for CH3CH(NH2)CH2OH is shown below.

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Give the formulae for the species responsible for peak 1 and peak 2 in the mass
spectrum.

peak 1

peak 2

[2]

(b). The teacher synthesises 2-aminopropan-1-ol, CH3CH(NH2)CH2OH, from 2-chloropropan-1-ol,

CH3CHCl CH2OH.

i. State the reagents and conditions required for this synthesis.

[1]

ii. The sample prepared by the teacher from 2-chloropropan-1-ol is not pure. It also
contains compound D.

Compound D has a molecular formula of C6H15NO2.

Suggest the structure of compound D.

Compound D

[1]
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(c). In a separate experiment, the chemistry teacher prepares compound E from 2-aminopropan-1-ol.

i. One of the functional groups in compound E is a phenol.

Name the other functional groups in compound E.

[1]

ii. Draw the structures of the two organic products formed when compound E is heated
under reflux with dilute hydrochloric acid.

[2]
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14(a). There are several isomeric alcohols with the formula C5H11OH.

Pentan-1-ol, CH3(CH2)3CH2OH, can be prepared in the laboratory by the reduction of an

aldehyde.

State a suitable reducing agent for this reaction and write an equation to show the preparation of
pentan-1-ol.
Use [H] to represent the reducing agent in the equation.

Reducing agent
....................................................................................................................................

Equation
................................................................................................................................................
[2]

(b). Compound F is a structural isomer of C5H11OH.

Compound F is converted to compound G when heated under reflux with acidified potassium
dichromate(VI) solution.

Compound G reacts with 2,4-dinitrophenylhydrazine to form an orange solid but compound G

does not react with Tollens’ reagent.

The 13C NMR spectrum of compound G is shown below.

Compound H is a carboxylic acid. In a titration, 0.211 g of carboxylic acid H requires 22.8 cm3 of
0.125 mol dm−3 NaOH for neutralisation.

Compound F reacts with compound H in the presence of concentrated sulfuric acid to form
organic compound I.

Identify compounds F, G, H and I and draw their structures in the boxes below.

Show your working only for the identification of compound H.

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(c). Compound J is another structural isomer of C5H11OH.

The 1H NMR spectrum of J is shown below.

The numbers next to each peak are the relative peak areas.

Identify compound J and draw its structure in the box below.

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15(a). i. State the region of the electromagnetic spectrum used in 1H NMR spectroscopy.

[1]

ii. Explain why CDCl3 is used as a solvent in 1H NMR spectroscopy.

[1]

(b). A student reacts compound K with 2,4-dinitrophenylhydrazine. An orange precipitate, L, was

formed.

The student purifies the orange precipitate, L, and sends the sample for analysis using 1H NMR
and 13C NMR spectroscopy.

The 13C NMR spectrum of L is shown below.

How many different carbon environments (types of carbon) are present in a molecule of
compound L?

[1]
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(c). The reaction of K to form L is repeated below.

The 1H NMR spectrum of L is shown below.

Use your answer to (c) and the data given to identify R1, R2 and the structure of compound L.

Explain how you used the chemical shifts and splitting patterns in the 1H NMR spectrum and any
evidence from the 13C NMR spectrum.

In the 1H NMR spectrum, HC–C=N– would have a peak in the range δ = 1.6–2.2 ppm.

In your answer, you should use appropriate technical terms, spelled correctly.
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(d). Draw the structure of compound K.

[1]

16(a). A chemist isolates compound H from a mixture and sends it for analysis.

Initial analysis shows that the molecular formula of compound H is C10H12O.

The 13C NMR spectrum of compound H contained eight separate peaks.

The 1H NMR spectrum of compound H is shown below.

1HNMR spectrum
The numbers by each peak are the relative peak areas.
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The 1H NMR spectrum contains a peak at δ = 0 ppm resulting from a chemical added to the
sample.

State the chemical responsible for the peak at δ = 0 ppm, and state why this chemical was added
to the sample.

[1]

(b). In the 1H NMR spectrum, the peak at δ = 3.7 ppm would normally be expected at a chemical shift
value about 1 ppm to the right, ie at 2.7 ppm.

Use the information in this question to determine the structure of compound H.

Show all your reasoning.

In your answer, you should use the appropriate technical terms, spelled correctly.
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[9]

17. The following three carbonyl compounds are structural isomers of C5H10O2.

Predict the number of peaks in the 13C NMR spectra of compounds C, D and E.

Compound C D E
Number of peaks

[1]

18(a). Alanine, serine and proline are α-amino acids.

A solution of serine was shaken with a few drops of D2O. The solution was then analysed using
1H NMR spectroscopy.

Complete the table to predict the 1H NMR spectrum of serine after the addition of D2O.

1H NMR spectrum for serine

Chemical shift, δ / ppm Relative peak area Splitting pattern

[2]
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(b). Enalapril is a drug used in the treatment of high blood pressure.

i. On the structure above, mark each chiral centre with an asterisk (*).

[1]

ii. Suggest two benefits of using single stereoisomers in the synthesis of drugs such as
enalapril.

[2]

iii. Enalapril is broken down in the body by acid hydrolysis.

Draw the structures of the three organic products of the acid hydrolysis of enalapril.

[4]

iv. A scientist hydrolysed enalapril in the laboratory. The scientist then analysed the mixture
of products using GC–
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Explain how GC– enables the products to be identified.

[1]

19(a). Ethers are a homologous series of organic compounds containing the R−O−R functional group.
The structures and names of two ethers are shown in Fig. 4.1.

Draw the skeletal formula of the ether, 2-ethoxy-3-methylbutane.

[1]

(b). Ethers can be prepared by nucleophilic substitution of haloalkanes with alkoxide ions, RO−.

i. Alkoxide ions can be prepared by reacting sodium with an alcohol. A gas is also formed.

Write an equation for the formation of methoxide ions from sodium and an alcohol.

[1]

ii. Methoxyethane, shown in Fig. 4.1, can be prepared by reacting bromoethane,

CH3CH2Br, with methoxide ions, CH3O−.

Suggest the mechanism for the nucleophilic substitution of CH3CH2Br with CH3O−.

Show curly arrows, charges, relevant dipoles, and products.

[3]

iii. In this mechanism, explain how CH3O− ions have acted as a nucleophile.

State the type of bond fission that takes place.

[1]
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(c). 2-Ethoxypropane, shown in Fig. 4.1, is analysed by 1H NMR spectroscopy.

Complete the table to predict the 1H NMR spectrum of 2-ethoxypropane.

You may not need to use all the rows.

Chemical shift, δ/ppm Relative peak area Splitting pattern

[4]

(d). In organic reactions, alkoxide ions can also act as a base.

The diagram below shows an incomplete mechanism for the reaction of a diester with methoxide
ions, CH3O− (Step 1), followed by reaction of the intermediate with bromoethane (Step 2).

i. For Step 1, add curly arrows to show how CH3O− reacts with the diester to form the
intermediate.
In the box, draw the structure of the organic product formed in Step 2.

[3]

ii. Explain how CH3O− ions have acted as a base in this mechanism.

[1]

20. Information about a monobasic organic acid D is shown below.

• D reacts by both electrophilic substitution and electrophilic addition.

• The molecular formula of D is CxHyO2.
• The mass spectrum of D has a molecular ion peak at m/z = 148.
• The 13C NMR spectrum of D contains seven peaks.

Determine and draw a possible structure for D.

Explain your reasoning from the evidence provided.

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[5]

21. A scientist analyses a compound that is present in a sample of ink.

The results are shown below:

Elemental analysis by mass:

C: 58.80%; H: 9.87%; O: 31.33%

Mass spectrum
Molecular ion peak at m/z = 102.0

Infrared spectrum
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The numbers by the peaks are the relative peak areas.

From the Data Sheet, the peak centred at δ = 4.9 ppm would be expected at a chemical shift
value about 1 ppm to the right, i.e. 3.9 ppm.

Use the results to identify the unknown compound. Show all your reasoning.

[8]
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22. * A chemist isolates compound L, with empirical formula C3H6O, and sends a sample for analysis.
The analytical laboratory sends back the following spectra.

Mass spectrum
Molecular ion peak at m/z = 116.0.
1HNMR spectra
The numbers next to each signal represent the number of 1H responsible for that signal.
Two 1H NMR spectra were obtained: one without D2O and one with D2O added.

1H NMR spectrum with no D2O:

1H NMR spectrum with D2O added:

13C NMR spectrum:

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Use the information provided to suggest a structure for compound L.

Give your reasoning.

[6]

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