Name: _______________________________________________

Spectroscopy Problems
Date:

Time: 2 hours 39 minutes

Total marks available: 159
Total marks achieved: ______

Questions
Q1.
The organic product of the reaction between ethanoyl chloride and methylamine has the
formula

(Total for question = 1 mark)

Q2.
Kits for manufacturing biodiesel from vegetable oils and methanol are sold for home
use. The reaction which takes place may be represented by the following equation.

*(a) Describe any two of the main hazards when carrying out this reaction. What
precaution would you take to minimise the risk in each case?
(4)
Hazard
.............................................................................................................................................
.............................................................................................................................................
Precaution
.............................................................................................................................................
.............................................................................................................................................
Hazard
.............................................................................................................................................
.............................................................................................................................................
Precaution
.............................................................................................................................................
.............................................................................................................................................
(b) Suggest two environmental benefits of using these kits, despite the associated risks.
(2)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(Total for question = 6 marks)

Q3.
Propanoic acid reacts with methanol to form an ester. The structure of the ester is

(Total for Question = 1 mark)

Q4.
Which of the following methods may be used in a single step to make carboxylic acids?
A Hydrolysis of an ester with an alkali.
B Reaction of acidified potassium manganate(VII) with an alkene.
C Hydrolysis of a nitrile with hydrochloric acid.
D Reaction of an acyl chloride with ammonia.
(Total for question = 1 mark)

Q5.
Which of the following compounds would react with lithium tetrahydridoaluminate
(lithium aluminium hydride) and also with phosphorus(V) chloride (phosphorus
pentachloride)?
A CH3CH2CH2COOH
B CH3CH2COCH3
C CH3CH CHCH3
D CH2 CHCH2CH2OH
(Total for question = 1 mark)

Q6.
In the synthesis of an ester, the use of an acyl chloride and an alcohol gives a better yield
than the use of a carboxylic acid and an alcohol.
This is because the reaction between
A an acyl chloride and an alcohol is an equilibrium.
B an acid and an alcohol goes to completion.
C an acid and an alcohol requires a catalyst.
D an acyl chloride and an alcohol goes to completion.
(Total for question = 1 mark)
Q7.
Ethanal, CH3CHO, can be converted by a two-step synthesis into 2-hydroxypropanoic acid.

(Total for question = 1 mark)

Q8.
Ethanoic acid, CH3COOH, can be converted into ethanoyl chloride, CH3COCl, by the action of
A phosphorus(V) chloride.
B chlorine.
C dilute hydrochloric acid.
D concentrated hydrochloric acid.
(Total for question = 1 mark)

Q9.
Which of the following molecules is a methyl ester?
A CH3COOCH2CH3
B HCOOCH3
C CH3COCH2CH3
D CH3COCl
(Total for question = 1 mark)
Q10.
An example of a polyester is

(a) The two monomers needed to form this polymer are

(1)

(b) The type of reaction to form this polymer is

(1)
A
B
C
D

addition.
substitution.
condensation.
hydrolysis.

(Total for question = 2 marks)

Q11.
The following tests can be carried out on organic compounds.
A Warm with 2,4-dinitrophenylhydrazine.
B Warm with Fehling's or Benedict's solution.
C Add solid sodium carbonate.
D Add phosphorus(V) chloride, PCl5.
(a) Which test would give a positive result with propanoic acid but not with propan-1ol?
(1)
A
B
C
D
(b) Which test would give a positive result with propanoic acid and with propan-1ol?
(1)
A
B
C
D
(c) Which test would give a positive result with propanal but not with
propanone?
(1)
A
B
C
D
(Total for question = 3 marks)

Q12.
Butane-1,4-diol, HO(CH2)4OH, and benzene-1,4-dicarboxylic acid,

HOOC

COOH, react to form a

polyester.

(a) The repeat unit of the polyester is

(1)
A

(b) The type of reaction is

(1)
A hydrolysis.
B addition.
C substitution.
D condensation.
(Total for question = 2 marks)

Q13.
A section of a polymer is shown below. Which of the following monomers would form
this polymer?

HOCH2CH2OH and ClCOCH2CH2COCl

HOCH2CH2OH and HOOCCH2CH2COOH

ClCH2CH2COCl alone

HOCH2CH2COOH alone
(Total for question = 1 mark)

Q14.
Which of the following reagents could be used to produce propanamide,
CH3CH2CON2?
A Ammonia and 1-chloropropane
B Ammonia and propanoyl chloride
C Methylamine and 1-chloropropane
D Methylamine and propanoyl chloride
(Total for question = 1 mark)
Q15.
In order to make CH3CH2CONHCH3, you could use
A
CH3CH2COOCH3 + NH3
B
CH3CH2COCl + CH3NH2
C
CH3CH2COONa+ + CH3NH2
D
CH3CH2CONH2 + CH3NH2
(Total for question = 1 mark)

Q16.
A sequence of reactions for the production of lactic acid is shown below.

(a) (i) Name the type and mechanism of the reaction in step 2.
(2)
..............................................................................................................................................
(ii) Which two substances need to be added to ethanal to carry out the reaction in step 2?
(2)
..............................................................................................................................................
..............................................................................................................................................
(iii) Give the mechanism for the reaction in step 2, using curly arrows to show movements
of electron pairs.
(3)

*(iv) The product of step 2 is not optically active even though it has a chiral carbon atom in its
formula.
Explain, by reference to the mechanism, the reason for the lack of optical activity.
(2)
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................

(b) What reactant, or combination of reactants, is needed to carry out step 3?

(1)
..............................................................................................................................................
(c) (i) What is the systematic name of lactic acid?
(1)
..............................................................................................................................................
(ii) Lactic acid molecules can combine to form a biodegradable polymer, poly(lactic acid) or
PLA.
Draw a section of the polymer with two units of the polymer chain and showing all
bonds.
(1)

(iii) Suggest why PLA is biodegradable.

(1)
..............................................................................................................................................
..............................................................................................................................................
(iv) Lactic acid can be prepared from ethene as shown in the scheme. Lactic acid also
forms when milk turns sour.
Suggest one reason why it would be advantageous to make lactic acid from milk rather than
from ethene.
(1)
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
(Total for question = 14 marks)

Q17.
This question is about four organic compounds, each containing two carbon atoms.
A

CH3CH2OH

CH3CHO

CH3COOH

CH3COCl
(a) Which is oxidized by ammoniacal silver nitrate?

(1)

A
B
C
D
(b) Which has the highest boiling temperature?

(1)

A
B
C
D
(c) 0.01 mol of each compound is heated separately with excess acidified sodium
dichromate(VI).
Which compound reduces the largest amount of sodium dichromate(VI)?
(1)
A
B
C
D
(d) 0.01 mol of each compound is added separately to identical volumes of water. Which
solution would have the lowest pH?
(1)
A
B
C
D

(Total for question = 4 mark

Q18.
Four organic compounds are:
A

CH3OH

HCHO

HCOOH

HCOOCH3

(a) Which of these compounds has a fruity smell?

(1)
A
B
C
D

(b) 0.01 mol of each compound is added separately to identical volumes of water.
Which solution would have the lowest pH?
(1)
A
B
C
D

(c) 0.01 mol of each compound is heated separately with excess acidified sodium
dichromate(VI) solution. Which compound reduces the largest amount of sodium
dichromate(VI)?
(1)
A
B
C
D

(d) Which compound has the highest boiling temperature?

(1)
A
B
C
D

(e) Which of these compounds can be oxidized by ammoniacal silver nitrate?

(1)
A
B
C
D

(Total for question = 5 marks)

Q19.
The equation for the reaction between ethanoic acid and phosphorus(V) chloride is
A
CH3COOH + PCl5 CH3COCl + POCl3 + HCl
B
CH3COOH + PCl5 CH3COOCl + PCl3 + HCl
C
CH3COOH + PCl5 CH3COCl + PCl3 + HOCl
D
2CH3COOH + PCl5 (CH3CO)2O + PCl3 + H2O + Cl2
(Total for question = 1 mark)

Q20.

Select from A to D the compound that

(a) forms iodoform with iodine in the presence of alkali.
(1)
A
B
C
D
(b) is chiral.
(1)
A
B
C
D
(c) reacts with Tollens' reagent.
(1)
A
B
C
D
(d) can be oxidized to form a ketone.
(1)
A
B
C
D
(Total for question = 4 marks)

Q21.
Which of these is not observed when ethanoyl chloride reacts with water?
A Misty fumes given off.
B The gas given off turns damp blue litmus paper red.
C The mixture gets hot.
D A white precipitate forms.
(Total for question = 1 mark)
Q22.
This question is about the four organic substances shown below.
A CH3CH2CH2CH2CHO
B CH3CH2CH2CH2COOH
C CH3COCH2CH2CH3
D CH3CH2CH2CH2COCl
Which substance will
(a) give a positive result with both Brady's and Tollens' reagents?
(1)
A
B
C
D
(b) be formed by the oxidation of a secondary alcohol?
(1)
A
B
C
D
(c) form the most acidic solution when equal amounts are each mixed with 100 cm3 of water?
(1)
A
B
C
D
(d) form steamy fumes in the reaction with PCl5?
(1)
A
B
C
D
(Total for question = 4 marks)
Q23.

Which of the following is a redox reaction?

A Ethanal reacting with Tollens' reagent.
B Ethanoyl chloride reacting with ammonia.
C Ethanoic acid reacting with ethanol.
D Ethanoic acid reacting with sodium hydroxide.
(Total for question = 1 mark)
Q24.
A flow chart for making 2-hydroxy-2-methylpropanoic acid from propan-2-ol is shown below.

(a) (i) Give the reagents and conditions for Step 1.

(2)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(ii) Propanone is formed in Step 1.
Give a chemical test to identify the carbonyl group and a further test to show the presence

of the
group.
For both tests, give the observations that you would make.
(4)

Carbonyl group
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................

group
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(b) (i) In Step 2, propanone undergoes an addition reaction with HCN in the presence of CN
ions.
Give the mechanism for this reaction.
(3)

(ii) Explain why this reaction would not take place at either a very low or very high pH.
(2)
Low pH
.............................................................................................................................................
.............................................................................................................................................
High pH
.............................................................................................................................................
.............................................................................................................................................
(c) (i) The reaction in Step 3 forms 2-hydroxy-2-methylpropanoic acid, (CH3)2C(OH)COOH.
Suggest the type of reaction occurring in Step 3.
(1)
.............................................................................................................................................
(ii) Explain why the presence of the alcoholic hydroxyl group cannot be confirmed in the
infrared spectrum of 2-hydroxy-2-methylpropanoic acid.
(1)
.............................................................................................................................................
.............................................................................................................................................
(iii) The hydrogen of the alcohol group in 2-hydroxy-2-methylpropanoic acid can be identified
by a single peak in the nmr spectrum.
Give the chemical shift you would expect for this peak.
(1)
.............................................................................................................................................
(iv) How many peaks would you expect in a high resolution nmr spectrum for 2-hydroxy-2methylpropanoic acid, (CH3)2C(OH)COOH?
(1)
.............................................................................................................................................
(v) Explain why, in high resolution nmr, the peak due to the hydrogens of the 2-methyl group
in 2-hydroxy-2-methylpropanoic acid is a singlet.
(1)
.............................................................................................................................................
.............................................................................................................................................

(vi) Would you expect 2-hydroxy-2-methylpropanoic acid to have optical isomers?

Justify your answer.
(1)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(d) (i) Molecules of 2-hydroxy-2-methylpropanoic acid react together to form a condensation
polymer.
Draw a displayed formula for this polymer, showing two repeating units.
(2)

(ii) Give the name of the functional group that links the two molecules in the polymer.
(1)
.............................................................................................................................................
(Total for question = 20 marks)

Q25.
Consider the four compounds shown below.
A

CH3COOCH3

CH3COOH

CH3CONHCH2CH3

CH3COCl

Which of these compounds

(a) will react most vigorously with water?
(1)
A
B
C
D
(b) forms methanol when refluxed with aqueous sodium hydroxide?
(1)
A
B
C
D
(c) has at least one triplet in its high resolution proton nmr spectrum?
(1)
A
B
C
D
(Total for question = 3 marks)

Q26.
The spectra of the compounds with the formulae CH3CH(OH)CH3 and CH3CH2CH2OH can be
distinguished by
A the value of m/e of the molecular ion in the mass spectrum.
B the presence of a fragment with m/e =15 in the mass spectrum.
C the presence of an absorption peak due to OH in the infrared spectrum.
D the number of peaks in the nmr spectrum.
(Total for question = 1 mark)
Q27.
An organic compound, X, was analyzed in a laboratory.
(a) Compound X was found to have the following percentage composition by mass:

(i) Use these data to calculate the empirical formula of compound X, showing your
working.
(2)
(ii) The mass spectrum of X is shown below.

Use your answer to (a)(i), and the mass spectrum of X, to show that the molecular formula
of compound X is C4H8O2.(2)

(b) The infrared spectrum of X has a broad peak at approximately 3500 cm1 and a sharp
peak at approximately 1700 cm1. Identify the bond responsible for the peak at
(2)
3500 cm

1700 cm1

(c) (i) Some chemical information about compound X is given below.

X is a neutral organic compound.

X has no effect on Tollens' reagent.

X turns hot acidified potassium dichromate(VI) solution from orange to green.

What does each of these three pieces of information suggest about the nature
of X?
(4)

.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(ii) Use your answers to parts (b) and (c)(i) to name the two functional groups present in
X.
(1)
.............................................................................................................................................

*(d) The high resolution proton nmr spectrum of X is shown below.

The relative number of protons causing the peaks shown are: J = 1, K = 1, L = 3 and M = 3.
Use the information above to determine the structural formula of X.
In your answer, you should refer to the number of peaks, their relative sizes and their
splitting patterns.
(7)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
..........................................................................................(Total for question = 18 marks)

Q28.
This question is about the reactions of butanoic acid, CH3CH2CH2COOH. It has a foul smell and
behaves like a typical carboxylic acid.
(a) (i) The addition of sodium carbonate solution is often used as a chemical test to distinguish
carboxylic acids, like butanoic acid, from other compounds, such as aldehydes.
Explain why old stocks of aldehydes often react with sodium carbonate solution.
(1)
.............................................................................................................................................
.............................................................................................................................................
(ii) How would the result of this test distinguish between a carboxylic acid and an old stock of
an aldehyde?
(1)
.............................................................................................................................................
.............................................................................................................................................
(iii) Write the balanced chemical equation, including state symbols, for the reaction of sodium
carbonate solution with butanoic acid.
(2)

*(iv) Infrared spectroscopy is a good physical method to distinguish carboxylic acids from other
organic compounds. Give the wavenumbers of two characteristic absorptions for a carboxylic
acid. Indicate the bond responsible for each absorption. Suggest why one of the absorptions is
broad.
(3)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................

(v) High resolution nuclear magnetic resonance spectroscopy is a suitable physical method to
use alongside infrared spectroscopy to identify butanoic acid. State the total number of peaks
and suggest the splitting pattern for each peak that you would expect for butanoic acid,
CH3CH2CH2COOH.
(3)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(b) Sketch the titration curve obtained when 50 cm3 of 0.10 mol dm3 sodium hydroxide solution
is added to 25 cm3 of 0.10 mol dm3 butanoic acid.
(4)

(c) (i) What would you see when phosphorus pentachloride, PCl5, reacts with butanoic acid?
(1)
.............................................................................................................................................
.............................................................................................................................................
(ii) Give the structural formula and name of the organic product of this reaction.
(2)
Structural formula

Name
.............................................................................................................................................
(d) (i) Give the name or formula of the organic product of the reaction between butanoic acid
and lithium tetrahydridoaluminate (lithium aluminium hydride).
(1)
.............................................................................................................................................
(ii) Water cannot be used as the solvent in this reaction because it reacts with lithium
tetrahydridoaluminate. Suggest a suitable solvent.
(1)
.............................................................................................................................................
(iii) State the type of reaction that takes place between butanoic acid and lithium
tetrahydridoaluminate. Justify your classification.
(2)
Type
.............................................................................................................................................
Justification
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................

(e) (i) Butanoic acid can be reacted with methanol to make methyl butanoate. State two
conditions that help to speed up this reaction.
(2)
.............................................................................................................................................
.............................................................................................................................................
(ii) Draw the displayed formula of methyl butanoate.
(1)

(iii) Identify another chemical, by name or formula, which could be added to methanol to make
methyl butanoate.
(1)
.............................................................................................................................................
*(iv) Give two advantages and one disadvantage of using the reaction occurring in (e)(iii),
compared to the reaction in (e)(i), when making methyl butanoate.
(3)
Advantages
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
Disadvantage
.............................................................................................................................................
.............................................................................................................................................
(Total for Question = 28 marks)

Q29.
An organic compound, Q, is found to contain 49.3% carbon and 6.8% hydrogen by mass.
(i) Use these data to confirm its empirical formula is C3H5O2.
(3)

(ii) The structure of Q is shown below.

The table below summarises some information about parts of the nmr spectrum of
compound Q.
Use the Data Booklet, and your knowledge of splitting patterns, to complete the table with
respect to the features of compound Q shown in bold.
(4)

Q30.
This question is about compounds X, C4H10O, and Y, C4H8O.
(a) Compound X, C4H10O, can be oxidized to compound Y, C4H8O. The infrared
spectrum of X is given below.

What can be deduced about the structures of X and Y using all this information and
the data booklet? Justify your answer.
(4)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................

(b) Below are the nmr spectra of X and Y.

*Use these nmr spectra and your answer to (a) to deduce the structural formulae of X

and Y. Justify your answer and explain why both nmr spectra are consistent with
these structures.
(6)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(Total for question = 10 marks)

Q31.
The carboxylic acid, propanoic acid, can be prepared by oxidation of the alcohol, propan-1ol.

(a) (i) Identify a suitable oxidizing agent you could use in this reaction.
(1)
.............................................................................................................................................
(ii) If you carried out this preparation in the laboratory, describe two measures you would take to
ensure the maximum possible yield of propanoic acid is obtained.
(2)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(iii) Propanoic acid can be made by the hydrolysis of a nitrile. Give the structural
formula of the nitrile and write an equation for this reaction.
(3)
Structural formula
.............................................................................................................................................
Equation

*(b) Propanoic acid reacts with methanol, CH3OH, to form the ester, methyl propanoate.
Even with the use of a catalyst, this reaction is quite slow and incomplete. Suggest a reagent, to
replace the propanoic acid, which would form the ester at a faster rate.
Suggest two reasons why your chosen reagent reacts faster.

(3)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(c) The structure of methyl propanoate can be investigated by using high resolution
1
H nuclear magnetic resonance (nmr) spectroscopy.
(i) What type of radiation interacts with 1H nuclei in nmr spectroscopy?
(1)
.............................................................................................................................................
(ii) Describe what happens to 1H nuclei when they absorb this radiation.
(2)
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(iii) Complete the table to show values for the chemical shift of the different 1H nuclei in methyl
propanoate and their splitting pattern. Page 7 of the data booklet gives information about
chemical shifts.
(2)

(Total for question = 14 marks)