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Class Reg Number

Candidate Name .......................................................................

Chemistry H2 9746
Tutor Tutee
Revision Exercise 20: Paper 2 Revision

1 Ionic compounds consist of cations whose total positive charge is balanced by the negative
charge of anions. However, a new class of compounds called electrides have been
synthesised that have ‘trapped’ or localised electrons taking on the role of anions.
Electrides are being studied as they have unusual properties not normally found in ordinary
salts.

Electrides have the general formula M+(L)ne-, in which e- represents the trapped electron,
M+ is an alkali metal cation and L is an organic molecule that binds the cation in a cage.

(a) Crown ethers are a group of synthetic large-ring polymers which are cyclic polymers of
ethane-1,2-diol and are named in the form x-crown-y, where x is the total number of atoms
in the ring and y is the total number of oxygens.

(i) Write an equation to show the formation in solution of an electride from a caesium atom
and two molecules of the crown ether, 15-crown-5, represented by 15C5. Use the state
symbol (solv) to indicate salvation by a non-aqueous solvent.

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(ii) Calculate the mass of caesium metal needed to react with 5.0 cm 3 of the crown ether,
15C5.

[Mr 15C5 = 220, Cs = 132.9, density of 15C5 = 1.1 g cm-3]

(iii) Calculate the theoretical yield in cm3 of the electride product (density 1.30 g cm-3) formed
from the above reaction.
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(b) A generalised Born-Haber cycle for electrides is shown below, where M is the metal, L is a
ligand and e- is an electron.
overall
L(s) + M(s) M+Le-(s)
sublimation

lattice
M(g) formation

solution ionisation
M+L(g) + e-
M+(g) + e-

solvation desolvation

complexation
L(aq) + M(aq) M+Le-(aq)

Cryptands are similar to crown ethers but have a third organic chain attached to two
trivalent nitrogen atoms. The prefix numbers of a cryptand name indicate the number of
oxygen atoms in each of the three chains.

(i) Explain what is meant by the term standard enthalpy change of formation.

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(ii) Using the data tabulated below, construct a Born-Haber cycle and calculate a value for the
enthalpy of formation of Cs+(C222)e-(s) from Cs(s) and C222(s), where C222 is a cryptand.
θ
Equations ∆ H / kJ mol-1
Cs(s) → Cs(g) +76.6
Cs(g) → Cs+(g) + e- +378.1
C222(s) → C222(g) +54.3
Cs+(g) + C222(g) → Cs+(C222)(g) -276.5
Cs+(C222)(g) + e- → Cs+(C222)e-(g) -292.3

2 Sulphur hexafluoride, SF6, was first synthesised by Henri Moissan in 1900 by burning
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sulphur in fluorine gas. The synthesis involves breaking the weak S–S and F–F covalent
bonds followed by the formation of strong S–F bonds, making the process extremely
exothermic.

(a)(i) Write an equation to show the standard enthalpy change of formation of sulphur
hexafluoride from fluorine and sulphur molecules (S8).

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(ii) Calculate an approximate value for the standard enthalpy change of formation of sulphur
hexafluoride using the following bond dissociation energies.

S–S 264 kJ mol-1 F–F 158 kJ mol-1 S–F 156 kJ mol-1

(b) The industrial synthesis of SF6 involves the combustion of molten sulphur in fluorine gas.
The product is contaminated with traces of disulfur decafluoride (S2F10). To remove the
impurity, the product is heated to 500oC at which temperature it disproportionates.

S2F10 (g) → SF6 (g) + SF4 (g)

(i) Draw a labelled sketch of the bonding present in SF 4 and SF6, showing bond angles and
the molecular shapes where appropriate.

(ii) Predict whether PF5 would be expected to be more or less chemically reactive than SF6.
Explain your answer with reference to the relative sizes of the central atoms of the two
molecules and the strength of the bonds formed with fluorine.

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(iii) Define the term disproportionation.

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(iv) Deduce the oxidation numbers for sulphur in all three sulphur containing species present
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during disproportionation of disulphur decafluroide.

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(c) Industrial production has resulted in atmospheric concentrations increasing rapidly over the
past 45 years. In 1978, the level of SF6 in the atmosphere was 0.6 ppt (parts per trillion,
where 1 trillion is 1012) and by 1998, the level had reached 4 ppt.

(i) Calculate the number of SF6 molecules present in 1 dm3 of the atmosphere measured at
273 K, 1 atmospheric pressure and at s.t.p. in the year 1978.

(ii) Calculate the total percentage increase in the SF6 concentration in the atmosphere from
1978 to 1998.

(iii) Assuming the current rate of increase remains constant, calculate the SF 6 concentration in
the atmosphere by 2010.

3 Coffee is a highly popular drink as it provides a pleasant-tasting and warming drink. The
delicious aroma of roast coffee beans has been found to contain over 800 different
compounds. They include melanoidins, citric acid and a class of polyhydroxy compounds
called chlorogenic acids, as shown below.
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(a) Draw the structures of the organic product(s) when chlorogenic acid is reacted with the
following compounds, stating also the type of reaction undergone.

(i) Aqueous bromine,

(ii) Acidified 2,4-dinitrophenylhydrazine,

(iii) Phosphorus(V) chloride,

(iv) Cold, dilute potassium manganate(VII)

(v) Excess aqueous sodium hydroxide in reflux.

(b) Chlorogenic acid, C16H18O9, behaves effectively as a weak monobasic acid according to the
equation:

C16H18O9 (aq) + H2O (l) ⇌ H3O+ (aq) + C16H17O9- (aq)

[Ka = 3.00 x 10-4 mol dm-3]

For 250 cm3 of solution containing 3.54 g chlorogenic acid, calculate

(i) The concentration of chlorogenic acid in mol dm-3,

(ii) The pH of the chlorogenic acid solution.

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(iii) A 15 cm3 sample of the chlorogenic acid solution is titrated with 0.02 mol dm-3 aqueous
sodium hydroxide. Calculate the volume of sodium hydroxide solution needed to react with
the chlorogenic acid present.

(iv) Predict the pH at the equivalence point, explaining your answer.

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(v) Hence, sketch a graph showing the change in pH when 0.1 mol dm-3 aqueous chlorogenic
acid is gradually added to 10 cm3 of 0.1 mol dm-3 aqueous barium hydroxide solution.

(c) Tea leaves contain about 4% by mass of caffeine while coffee beans contain between 1 to
2%. Caffeine has the molecular structure as shown below. Another similar compound is
adenosine found in DNA.

Describe a chemical test to distinguish between both compounds, stating any observations.
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(d) When coffee beans or tea leaves are immersed in hot water, the concentration of caffeine
increases with time. The concentration c rises rapidly initially, but then increases at a
slower rate before reaching a constant value c∞ at equilibrium.

Research on coffee has shown that that the rate constant, k, does not depend on the
degree of stirring but rather k varies inversely with r2, where r is the radius of the ground
coffee particles, infusion is therefore faster the more finely the beans are ground; k
increases by roughly 3% for every 1oC rise in temperature.

(i) Sketch a graph of concentration of caffeine, c, against time t when coffee beans or tea
leaves are immersed in hot water.

(ii) If the radius r, of coffee beans in separate samples are reduced by a factor of half and a
quarter respectively, what will be the effect on the rates of infusion of caffeine, k?

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4(a) In the past decade, scientists have learnt that ancient DNA extracted from mummified
tissue samples of extinct animals and even fossils can be analysed. Tris (hydroxymethyl)
aminomethane, or tris, is a biochemical buffer whose buffering range is pH 7 to 9 and K b is
1.19 x 10-6 for the following reaction.

(HOCH2)3CNH2 (aq) + H2O (l) ⇌ (HOCH2)3CNH3+ (aq) + OH- (aq)

Tris TrisH+

(i) Explain what is meant by the term buffer.

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(ii) With reference to the buffering range of tris, account for its basicity.
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(ii) The optimum pH of blood is 7.40. Calculate the ratio of tris / trisH+ at this pH.

(iii) Calculate the pH after 1 cm3 of 6 mol dm-3 HCl(aq) is added to a 200 cm3 sample
of the pH 7.4 tris buffer.

(b) The bleach solution used in ancient DNA laboratories contains sodium
hypochlorite, NaClO.

(i) With the aid of an equation, outline the procedure for making a solution of sodium
hypochlorite in the laboratory.

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(ii) Calculate the number of moles of sodium hypochlorite in 100 cm3 of 20% industrial strength
bleach solution, whereby 20% means 20 g of NaClO is present in 100 cm3 of bleach
solution. Hence, calculate the concentration of the bleach solution of NaClO.
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(iii) Suggest why ancient DNA researchers take care not to mix bleach solution with acid.

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Industrial strength bleach is unstable and on standing, particularly in sunlight, evolves

oxygen.

(iv) Write an equation for the above reaction.

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(v) Suggest how bleach should be stored in ancient DNA labs to minimise its decomposition.

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(c) Another buffer system in the blood involves carbonic acid and hydrogencarbonate. When
carbon dioxide is dissolved in water, the following equilibria are established:

The first and slowest step in the reaction is the dissolution of the gas:

CO2 (g) ⇌ CO2 (aq)

The next reaction produces hydrogencarbonate ions

CO2 (aq) + H2O (l) ⇌ H+ (aq) + HCO3- (aq)

which then dissociate to give carbonate ions,

HCO3- (aq) ⇌ H+ (aq) + CO32- (aq)

The table below shows some physical properties of pure carbon dioxide under commercial
carbonating conditions.

Molar mass 44.01 g mol-1

Vapour pressure (15oC) 5.085 x 106 Pa
Density of gas (15oC) 1.85 g dm-3
Temperature 31.1 oC
Pressure 7.383 x 106 Pa
Solubility of gas in water (15 C, 105 Pa)
o
1.98 g dm-3

The relationship between gas pressure and concentration of mass of dissolved carbon
dioxide is given by Henry’s Law:

PCO2 = Kh[CO2(aq)]

Where PCO2 represents the partial pressure of CO2 above the drink, [CO2(aq)] the
concentration of dissolved CO2 gas and Kh, the Henry’s law constant for CO2.

Henry’s Law states that the amount of gas dissolved in a solution is directly proportional to
the pressure of the gas in the head space above the solution.

(i) It was found that Henry’s Law is not exactly obeyed by carbon dioxide, especially under
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commercial carbonating conditions. With reference to the data above, explain why Henry’s
Law may not be obeyed under them.

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(ii) Suggest why the solubility of carbon dioxide and nearly all other gases decreases with
increasing temperature.

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The Henry’s Law constant, Kh, for carbon dioxide in water at 25oC is 3.8 x 10-2 mol dm-3
atm-1.

(iii) Air contains 0.0035% of carbon dioxide by volume. Calculate the solubility in mol dm -3 of
carbon dioxide at 25oC.

(iv) A fizzy drink is produced in a factory using a carbonating process which supplies carbon
dioxide at a pressure of 12 atmospheres. Calculate the volume of carbon dioxide measured
at 25oC and 1 atmosphere that would be dissolved in a 500 cm3 bottle of the carbonated
drink, assuming that Henry’s Law is obeyed.

(v) Assuming Henry’s Law is obeyed by carbon dioxide, deduce the pH change of the resulting
carbonated drink if the pressure is doubled from 12 to 24 atmospheres.

5 In recent years, there has been a growing demand for reduced alcohol-beers but
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unfortunately ethanol (alcohol) is a major contributor to beer flavour and drinkability and so
beers that contain very little alcohol will taste very different from one containing the usual 4
to 5% alcohol, but beers contain many other substances that contribute to their flavour
which must be taken into account when producing low-alcohol beers.

(a) A typical Australian beer contains 5% ethanol by volume. Given that the densities of
ethanol and water are 0.789 and 0.998 g cm-3 respectively, calculate

(i) The concentration of ethanol in mol dm-3,

(ii) The number of ethanol molecules present in a pint of low alcohol beer that contains 1% by
volume of ethanol.

[1 dm3 = 1.8 pints, Avogadro’s constant = 6.02 x 1023 mol-1]

(b) Bacteria like yeast used in the fermentation of glucose to ethanol contain a ‘proton pump’ to
absorb sugars and other nutrients. The simplest method of restricting the amount of alcohol
produced during fermentation is to use strains of yeast that are unable to convert the
sugars that brewing yeasts would use to convert to alcohol.

(i) Account for the higher than expected pH of a low-alcohol beer (ethanol concentration less
than 1.2%) compared to that of a typical beer where the ethanol concentration is between 4
to 5.

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(ii) Although some beers are carbonated with dissolved carbon dioxide, this is not a significant
contributor to the low pH of beers. Comment on this statement.

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(c) Hops were first added to beer in the 15th century and not only give beer its bitter taste but
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also to add special flavours and aromas. Hops contain compounds that react on heating to
form other, even more bitter compounds. One such reaction, in which humulone is
converted to the extremely bitter compound, iso-humulone, is shown below.

(i) Examine the structure of iso-humulone and note the presence of two hydroxyl groups
within the molecule. Explain why the iso-humulone molecules do not undergo simple
oxidation when beer is left to stand in air.

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(ii) Account for the greater solubility of iso-humulone compared to humulone, despite the
presence of only two hydroxyl groups in the former.

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(iii) Bitterness is a flavour, not an aroma and cannot be smelt. Suggest why it is unlikely that
the R group (CH2CH(CH3)2) present in humulone and iso-humulone is the specific
functional group responsible for the bitter taste of beer.

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(iv) State the structural relationship between humulone and iso-humulone.

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(v) Predict if iso-humulone makes a significant contribution to the smell of beer, explaining
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your answer.

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9(a) Both esters and amides undergo acid-catalysed hydrolysis. The mechanism for the
hydrolysis of either functional group involves the following four steps:

• protonation;
• nucleophilic addition of water;
• proton transfer;
• elimination of an alcohol or an amine molecule.

For esters, the protonation that occurs during the first step produces the more stable cation
A rather than cation B.

(i) Suggest why cation A is more stable than cation B.

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The length of the C-N bond in amides (0.132 nm) is significantly shorter than an ordinary C-
N bond (0.147 nm). Furthermore, the amide group is planar.

(ii) Suggest an explanation for these observations.

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(iii) Use this information, together with your mechanism in part (i), to suggest why amides
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undergo hydrolysis at a much slower rate than esters.

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(b) Gel electrophoresis is often employed to analyze the mixtures of amino acids and small
peptides obtained by the hydrolysis of proteins. In a particular experiment, glycine,
H2NCH2COOH, is an amino acid obtained from the hydrolysis of a polypeptide protein
molecule.

(i) Using the amino acid glycine (H2NCH2COOH, isoelectronic point = 6.1) as an example,
explain how the pH of the solution used for electrophoresis can influence the results.

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The diagram below shows the result of carrying out electrophoresis on a sample of amino
acids obtained from hydrolyzing a protein.

Assuming all the amino acids shown above are overall singly charged species at a
particular operating pH,

(ii) which amino acid has the lowest relative molecular mass?

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(iii) which amino acid has a positive charge?

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7(a) The substance GHB was originally designed for use in sleeping pills. However, other drug-
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abuse issues were identified with the substance and its sale was restricted in 2003. GHB
stands for hydroxybutyric acid, an old name for the structure shown below.

(i) Name the two functional groups in GHB.

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(ii) Give the systematic name for GHB.

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(b) A substance known as GBL is converted into GHB in the body. The structure of GBL is
shown below.

GBL

(i) Name the functional group in GBL.

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(ii) Name the type of reaction by which GBL forms GHB in the body.

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(iii) Describe a chemical test to distinguish between GHB and GBL, stating any observations.

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(c) GHB is a weak acid. Weak acids can be represented as HA.

(i) Write an equation to show how a weak acid HA behaves when dissolved in water.

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(ii) Use ions and molecules from this equation to explain the meaning of the term conjugate
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base.

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(iii) Write an expression for the acidity constant Ka of an acid HA.

(iv) A 0.10 mol dm–3 solution of GHB has a pH of 2.9.

Calculate the value of Ka for GHB and give its units.

(v) State one simplifying assumption that you made when carrying out your calculation in (iii).

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(d) A mixture of GHB and its sodium salt acts as a buffer solution.

(i) Explain the meaning of the term buffer solution and explain why buffer solutions are found
in our bodies.

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(ii) Calculate the pH of a buffer solution containing equal amounts of GHB and its sodium salt.

8(a) Explain what is meant by ligand exchange.

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(b) Describe all the colour changes and observations that take place when an aqueous
solution of ammonia is gradually added to a solution of Cu2+(aq), until the ammonia is in
excess. Write equations for these transformations.

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(c) Blood gets its colour from oxygen-carrying molecules with organic groups surrounding a
transition metal ion. In humans this transition metal is iron, and the blood is red. In
horseshoe crabs, the metal is copper and the blood is blue, and in sea squirts the metal is
vanadium and the blood is green.

The sketch below shows the major absorption peak for human blood.

On this sketch, show and label the corresponding absorption peaks for the blood of
horseshoe crabs and sea squirts. Explain your answer.

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(d) A 0.0100 mol sample of an oxochloride of vanadium, VOCIx required 20.0 cm3 of 0.100 mol
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dm-3 acidified potassium manganate(VII) for oxidation of the vanadium to its +5 oxidation
state.

Deduce the value of x in the formula VOCIx.

End of Paper