2

1 Planning (P) For

Examiners
use

Weak organic acids such as tartaric acid, malic acid, lactic acid, acetic acid and citric acid,
are significant constituents in determining the sensory properties of wines and beverages.
Soft drinks often contain varying quantities of several acids, which give sodas their tart
flavour.

Acids can be classified as monobasic, dibasic, or tribasic, depending on how many protons
donated to the base during neutralization.

In sodas such as Sprite and 7-Up, the acids are carbonic acid (from carbonated
water) and citric acid.
Citric acid, C6H8O7, reacts with NaOH(aq) in one of the following ways:

C6H8O7(aq) + NaOH(aq) NaC6H7O7(aq) + H2O(l)

C6H8O7(aq) + 2NaOH(aq) Na2C6H6O7(aq) + 2H2O(l)
C6H8O7(aq) + 3NaOH(aq) Na3C6H5O7(aq) + 3H2O(l)

You are to plan a titration to determine which of the above equations correctly
represents the neutralisation between citric acid and NaOH.

You are provided with a can (330 cm3) of 7-Up which has been opened so that it
is decarbonated and you can assume that the only acid present is citric acid and
its concentration is 0.0420 mol dm-3;
Solid NaOH;
Deionised water.
You are also provided with the standard apparatus present in the laboratory.

(a) A standard aqueous NaOH solution may be prepared using solid NaOH so that it can
be titrated with citric acid. Suggest an appropriate concentration of the standard
aqueous NaOH solution to be prepared. Show your working.

[You are to assume that the pipette provided has a capacity of 25.0 cm3 and that
10.00 cm3 titre values 35.00 cm3]

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[2]
(b) Outline, step by step, how you would prepare, in a graduated flask, 250 cm3 of an For
Examiners
aqueous solution of NaOH with exactly the concentration you have given in (a). use

[Ar: Na,23.0; H,1.0; O,16.0]

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[4]

(c) Draw a labelled diagram of the apparatus you would use to titrate the citric acid in For
Examiners
7-Up with the standard aqueous NaOH solution which you have prepared. The use
following details should be included in your labels:
the volume of citric acid used
name and capacity of apparatus used.

[1]

(d) Suggest a suitable indicator to be used during this titration and state the colour
change observed at end-point of the titration.

[1]

(e) Draw up tables with appropriate headings to show the data you would record in (b)
and (c).

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[1]

(f) Assuming that the average titre of NaOH used is y.00 cm3, show how you would
process the results to find the correct equation for the neutralisation reaction
between citric acid and NaOH.

[1]

(g) If the result shows that citric acid is tribasic and given the following informations:
citric acid is a tertiary alcohol,
citric acid is optically inactive,
draw a possible structural formula of citric acid.

[1]

(h) Identify a safety risk in the experiment and explain how you would minimise it when
carrying out the experiment.

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[1]

[Total: 12]

2 (a) The use of the Data Booklet is relevant to this question. For
Examiners
The nitrates, carbonates and hydroxides of Group II elements can undergo thermal use
decomposition.

(i) Write a balanced equation, with state symbols, for the decomposition of calcium
nitrate.

(ii) The nitrates of lead and zinc can undergo thermal decomposition similar to
calcium nitrate. The decomposition temperatures of the three nitrates are given in
the following table.

Compound decomposition temperature / C

Lead(II) nitrate, Pb(NO3)2 290

Zinc nitrate, Zn(NO3)2 105

Calcium nitrate, Ca(NO3)2 132

Explain the data in the table by quoting relevant values from the Data Booklet
and using your understanding of the trend in the decomposition temperatures of
the Group II nitrates.

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[4]

(b) Another Group II compound, magnesium chloride, MgCl2, is an important coagulant used For
Examiner
in the preparation of soy products. s use

The lattice energy of MgCl2 can be calculated from a BornHaber cycle using the following
data and others found in the Data Booklet.

Enthalpy change of atomisation of magnesium +147 kJ mol-1

Enthalpy change of formation of magnesium chloride, -641 kJ mol-1
MgCl2(s)
First electron affinity of chlorine -364 kJ mol-1
Enthalpy change of atomisation of chlorine +122 kJ mol-1

(i) Define, with the aid of an equation, the lattice energy of MgCl2.

(ii) Construct a Born-Haber cycle for the formation of MgCl2 and use it to calculate
the lattice energy of MgCl2.

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(iii) Explain how you would expect the numerical magnitude of the lattice energy of For
Examiner
BaCl2 to compare with that of MgCl2. s use

(iv) The enthalpy change of formation of a hypothetical ionic solid, MgCl,

is -125 kJ mol-1.
Using the data given above, calculate the enthalpy change of reaction, H reaction, for
the following reaction:

2MgCl (s) MgCl2(s) + Mg(s)

Hence comment on the stability of MgCl(s) relative to that of MgCl2(s).

[8]

(c) The solubility product of some Group II fluorides, at 25oC, are given in the table below:

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(i) Which of the above fluorides is most soluble and what is its solubility,
in mol dm-3, at 25 oC?

(ii) Briefly explain how the solubility of the fluoride in (c)(i) would change if it is For
Examiners
dissolved in an aqueous KF solution. use

[3]

(d) A researcher accidentally mixed 50.0 cm3 of 0.200 mol dm-3 CaCl2 solution with 25.0 cm3
of 0.100 mol dm-3 BaCl2 solution in the laboratory.

To separate the two metals ions, he added just enough solid KF to precipitate the
maximum amount of CaF2 from the mixture.

(i) Calculate the minimum concentration of fluoride ions required to cause

precipitation of BaF2.

(ii) Hence, calculate the concentration of Ca2+ ions in the solution when the first trace
of BaF2 appears.

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[3]

[Total: 18]

3 The addition of F2 to aqueous NaOH produces aqueous NaF and a triatomic gaseous For
Examiners
molecule, A. use
To produce a certain amount of A, a limited amount of F2 gas is added into 150 cm3 of
0.100 mol dm-3 of aqueous NaOH solution. At room temperature and pressure, the volume
of A collected is 142 cm3 and it weighs 0.324 g.
25.0 cm3 of the resultant solution is titrated against 0.0500 mol dm -3 of aqueous H2SO4
solution using methyl orange as an indicator. 15.00 cm 3 of H2SO4 was needed for
neutralisation.

(a) Calculate the number of moles of NaOH used to react with F2.

[2]
(b) (i) Using the ideal gas equation, calculate the Mr of A.

(ii) Hence, deduce the molecular formula of A.

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(iii) Explain why there is a difference between the theoretical Mr value of A and the
value calculated in (b)(i).

(iv) Construct a balanced equation for the formation of A from the reaction between For
Examiners
NaOH and F2. use

[5]

(c) The use of the Data Booklet is relevant to the following questions.

(i) By comparing the first four Ionisation Energies of F and O, explain the common
trend seen.

(ii) Briefly account for the difference in the Second Ionisation Energy values
between F and O.

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[4]

[Total: 11]

4 (a) Aqueous bromine is decolourised when added to aqueous sodium thiosulfate. For
Examiners
When excess of aqueous barium chloride is added to the resulting solution, a use
white precipitate is observed. This precipitate is filtered off, leaving a colourless
filtrate.

(i) Write a balanced ionic equation for the reaction between bromine and
sodium thiosulfate.

(ii) Identify the white precipitate.

(iii) To the colourless filtrate in (a) above, aqueous silver nitrate is added,
followed by dilute aqueous ammonia solution.

Describe what is observed and give the formula of the complex ion formed
after the addition of dilute aqueous ammonia solution.

[4]

(b) Aqueous bromine is added separately to aqueous potassium iodide and

aqueous potassium chloride. To the each of the resulting mixtures, an equal
volume of an organic solvent is added.

What will be the colour of the organic layer for each of the two mixtures?
Write equations, if any, for the reactions in the two mixtures.

Aqueous bromine + aqueous potassium iodide

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Aqueous bromine + aqueous potassium chloride

[3]

(c) Bromine that is obtained from sea water is blown out with air and then For
Examiners
absorbed in aqueous sodium carbonate. A solution of sodium bromate(V) use
and sodium bromide is produced in the ratio of 1:5.

(i) Write an ionic equation for the reaction of bromine with sodium carbonate.

(ii) The mixture is acidified and bromine is then distilled out. Construct the ionic
equation for the formation of bromine in this step.

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[2]

[Total: 9]

5 (a) The reaction scheme below shows the conversion of bromoethane to propanone:
(i) (ii)
CH3CH2Br B CH3CH2COOH
Reduce with LiAlH4
followed by dehydration

C
(iii)

(iv)

CH3COCH3
Give the reagents and conditions for the steps (i) to (iv) and identify B and D:

(i)

(ii)

(iii)

(iv)

B D

[6]

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(b) Aldehydes and ketones which possess at least one hydrogen on the neighbouring For
Examiners
carbon atom to the carbonyl group, (for example, CHCO), undergo the aldol addition use
in the presence of dilute solutions of bases.

OH
Dilute NaOH
2CH3COCH3 O
H3 C C CH 2 C

CH 3
H 3C

Predict the other products that will be formed when a mixture of propanone and
ethanal react with dilute aqueous sodium hydroxide.

[2]

[Total: 8]

6 Insulin is the hormone essential for carbohydrate metabolism. Partial hydrolysis of insulin
gives the following tripeptide

CH2CH2CO2H

(CH3)2CHCH(NH2)CONHCHCONHCH(CH3)CO2H

(a) (i) Draw the structural formulae of the constituent amino acids which could be
obtained by further hydrolysis of this tripeptide.

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(ii) In solution, amino acids exist as zwitterions. Use one of the constituent amino For
Examiners
acid produced by hydrolysis to illustrate what is meant by this term. use

(iii) How would you expect the melting point and the solubility in water, of an
unionized covalent form of the amino acid to compare with the actual properties
of the zwitterionic form?

(iv) In aqueous solution, amino acids can act as buffers. By means of an equation,
show how the given constituent amino acid can act as buffer when small
amount of dilute HCl is added to its solution.

[7]

(b) Analysis of a polypeptide E showed that the amino-(N-) terminal end is methionine
(met) and that the carboxyl-(C-) terminal end is lysine (lys).
Enzymic hydrolysis of the polypeptide produced the following tripeptides, with the
amino acid residue on the left having the free amino group.

gly-arg-val ala-gly-arg ala-gly-ala met-ala-gly arg-val-lys gly-ala-gly

Work out the sequence of amino acids in E, using the 3-letter abbreviations. Use
each tripeptide once only.

[2]

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(c) The following scheme of reactions illustrates the synthesis of a dipeptide, F: For
Examiners
use
(C6H5)3C-Cl + H2N-CH(CH3)-CO2H

step I

(C6H5)3C-NH-CH(CH3)-CO2H

step II

(C6H5)3C-NH-CH(CH3)-COCl

step III + NH2CH2CO2H

(C6H5)3C-NH-CH(CH3)-CO-NHCH2CO2H

step IV

(C6H5)3C-H + NH2-CH(CH3)-CO-NHCH2CO2H

(i) What type of reaction is step I?

(ii) Suggest a reagent for step II.

(iii) During which step is the peptide bond formed?

(iv) What are the reagents and conditions needed for the hydrolysis of F?

(v) Suggest the type of reaction in step IV.

[5]

[Total: 14]

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