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Class Reg Number

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

Chemistry H2 9746
Tutor Tutee
Revision Exercise 22: Integrated Questions

1 Aqueous copper(II) sulphate contains [Cu(H2O)6]2+ ions. Aqueous ammonia is added drop
by drop to a small volume of aqueous copper(II) sulphate. Two reactions take place, one
after the other, as shown in the equations.

[Cu(H2O)6]2+(aq) + 2OH–(aq) → Cu(OH)2(s) + 6H2O(l)

Cu(OH)2(s) + 2H2O(l) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 2OH–(aq)

(a) Describe the observations that would be made as ammonia is added drop by drop until it is
in an excess.

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(b) Draw the shape for the [Cu(H2O)6]2+ ion. Include the bond angles in your diagram.

(c) Water is a simple molecule. The H—O—H bond angle in an isolated water molecule is
104.5°.
The diagram shows part of the [Cu(H2O)6]2+ ion and the H—O—H bond angle in the
water ligand.

Explain why the H—O—H bond angle in the water ligand is 107° rather than 104.5°.

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L_A_Level Chemistry 2815 2005_01 Q3

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2 One cause of low-level smog is the reaction of ozone, O3, with ethene. The smog contains
methanal, CH2O(g), and the equation for its production is shown below.

O3(g) + C2H4(g) → 2CH2O(g) + ½O2(g) equation 2.1

(a) The rate of the reaction doubles when the initial concentration of either O3(g) or C2H4(g) is
doubled.

(i) State the order of reaction with respect to

O3 .......................

C2H4 .......................

(ii) Write the rate equation for this reaction.

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(b) For an initial concentration of ozone of 0.50 × 10–7 mol dm–3 and one of ethene of 1.0 × 10-8
mol dm–3, the initial rate of methanal formation was 1.0 × 10–12 mol dm–3 s–1.

(i) How could the initial rate of methanal formation be measured from a concentration/time
graph?

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(ii) Calculate the value of the rate constant and state the units.

(iii) The initial rate of methanal formation is different from that of oxygen formation in equation
2.1. Explain why.

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(iv) The experiment was repeated but at a higher temperature. What would be the effect of this
change on the rate and the rate constant of the reaction?

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(c) In the stratosphere, ozone forms when oxygen free radicals react with oxygen molecules.

O2 + O → O3

The oxygen free radicals are initially formed as diradicals when oxygen gas, O2, is
dissociated by strong ultraviolet radiation,

O2(g) → 2O(g)

(i) Suggest why oxygen free radicals, O, are often called diradicals.

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(ii) Draw a ‘dot-and-cross’ diagram of an ozone molecule. Show outer electrons only.

(iii) Chlorine free radicals formed from CFCs deplete the ozone layer in a chain reaction.
Typically, 1 g of chlorine free radicals destroys 150 kg of ozone during the atmospheric
lifetime of the chlorine free radical (one to two years).

Calculate how many ozone molecules are destroyed in this chain reaction by a single
chlorine free radical before the free radical is destroyed.

L_A_Level_Chemistry 2816_01 Jan 05 Q2

3 This question is about haemoglobin and the photosynthetic pigment chlorophyll-a. The
structure of chlorophyll-a is shown below.
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(a)(i) State one way in which the structure of chlorophyll-a is similar to that of haemoglobin.

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(ii) Suggest one way in which the structure of chlorophyll-a differs from that of haemoglobin.

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(b) Suggest the formula of one alcohol that would be released by hydrolysis of an ester group
in chlorophyll-a.

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(c) Describe the quaternary structure of haemoglobin.

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L_A_Level_Chemistry 2815_02 Q3
4 Unwanted metals can find their way into food, either from the soil or from machinery during
harvesting and processing. Ions of metals such as copper, iron and nickel catalyse the
breakdown of fats in food.

(a) Copper, iron and nickel are transition metals. What property of transition metals allows
them to behave as catalysts?

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(b) A class of food additives known as sequestrants can be used to remove these metal ions.

Typical sequestrants are the calcium and sodium salts of H4 edta.

The structure of the edta4– ion is shown below.

The edta4– ion acts as a hexadentate ligand. On the structure above, label with an asterisk
(*) the six sites that form bonds to the metal ion.
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(c) Underline the term below that describes the shape of the complex formed between a
nickel(II) ion and an edta4– ion.

linear octahedral square planar tetrahedral

(d) The reaction of edta4– ions with nickel(II) ions can be represented by the following equation.

[Ni(H2O)6]2+(aq) + edta4– (aq) ⇌ [Ni(edta)]2– (aq) + 6H2O(l)

(i) Write an expression for the equilibrium constant, K, for the reaction.

(ii) Equilibrium constants for ligand exchange reactions are usually called stability constants,
Kstab. The value of Kstab for the above reaction is 2.00 × 1019 mol–1 dm3 at 25 °C.

What does this tell you about the position of equilibrium at 25 °C? Explain your reasoning.

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(iii) The forward reaction in the above equilibrium is slightly exothermic. At temperatures higher
than 25°C, edta4– ions sequester nickel(II) ions less effectively. Explain why this is so.

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(e) The amount of nickel(II) ion in a solution can be found by titrating with a solution of edta4– of
known concentration using a suitable indicator.

25.0 cm3 of a solution containing nickel(II) ions reacted with exactly 22.0 cm3 of a 0.100 mol
dm–3 solution of edta4– ions.

Calculate the concentration of nickel(II) ions in the solution.

L_A_Level Chemistry 2849 Jan 05 Q5

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5 In your answers to the questions that follow, show all of your working.

At room temperature and pressure, r.t.p., 1 mol of gas molecules has a volume of 24 dm3.
Whilst digging his garden, a chemistry student found what appeared to be a piece of
bronze, possibly from the Bronze Age. The student knew that bronze was an alloy of
copper with other metals including tin. He carried out three experiments on samples of the
bronze.

(a) Experiment 1

He dissolved a small piece of the bronze, weighing 0.28 g, in concentrated (16 mol dm–3)
nitric acid, HNO3. 5 cm3 of a blue solution C containing Cu2+ ions was formed together with
a brown gas with the molecular formula NO2.

Equation 5.1 represents the equation for the reaction between copper and concentrated
nitric acid.

Cu + 4H+ + 2NO3– → Cu2+ + 2NO2 + 2H2O equation 4.1

The student analysed the blue colour from the Cu2+ ions in solution C using a colorimeter.
He found out that the concentration of Cu2+ ions in solution C was 0.68 mol dm–3.

The student concentrated the solution and obtained some blue crystals of a compound A
with a percentage composition by mass of Cu, 26.29%; N, 11.60%; O, 59.63%; H, 2.48%.
This composition included 3 waters of crystallisation.

(i) Calculate the percentage of copper in the bronze relic.

(ii) Calculate the empirical formula of A.

(b) Experiment 2

The student dissolved another small piece of the bronze relic in dilute (8 mol dm–3) nitric
acid. A blue solution containing Cu2+ ions was again formed but this time a colourless gas
was produced with the molecular formula NO. Equation 5.2 represents the unbalanced
equation for this second reaction.

Cu + H+ + NO3– → Cu2+ + NO + H2O equation 5.2

By considering oxidation numbers, balance equation 5.2.

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(c) Experiment 3

The student heated a third small piece of the bronze relic with concentrated sulphuric acid.
The copper in the bronze relic reacted to produce a blue solution and 90 cm3 of a gas B,
measured at r.t.p.. The mass of the gas B collected was 0.24 g.

(i) Suggest a possible identity of gas B.

(ii) Suggest a likely balanced equation for this reaction.

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L_A_Level Chemistry 2816_01 Jun 05

6 The scheme below shows the final stages in the synthesis of cypermethrin, which is widely
used today as an insecticide.

(a)

(i) Complete the structure of the organic compound C in the box above.
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(ii) Name the functional group that is formed in stage 3.

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(iii) Identify suitable reagents to carry out stage 2.

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(iv) State the type of chemical reaction occurring in stage 2.

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(b) One company manufacturing the insecticide uses an enzyme to catalyse the reaction in
stage 2. Cypermethrin made by this method can be used in smaller doses than
cypermethrin made by the normal laboratory conditions.

Suggest an explanation.

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(c) Cypermethrin does not remain on crops because it is broken down in the environment by
hydrolysis. It can also be rapidly hydrolysed in the laboratory using an acid catalyst.

(i) State how you would carry out acid hydrolysis of cypermethrin in the laboratory.

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(ii) Suggest the structures of two organic compounds that could be produced by acid
hydrolysis of cypermethrin.

A_GCE_Chemistry 2814_01 Jun 07

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7 Compounds A and B, which are isomers with molecular formula C6H12O4, react readily with
potassium carbonate under room conditions to give a colourless gas. Reaction of A and B
with hot acidified potassium manganate (VII) yields products C and D respectively.

C is optically inactive and gives an orange precipitate with 2,4-dinitrophenylhydrazine. With

alkaline aqueous iodine followed by acidification, C gives compound E, C5H6O5, which is a
symmetrical molecule.

D, another optically inactive molecule, has molecular formula C6H10O5. D reacts with excess
phosphorus pentachloride to form F with the evolution of vigorous white fumes. F reacts
with ethane-1,2-diol to give a compound G, a diester.

Deduce the structures of compounds A to F, explaining your reasoning.

8 Hydrocarbon U (Mr = 120) was isolated. Upon irradiation of U with uv light in the presence
of bromine gas, a product V is isolated. Upon heating with aqueous potassium hydroxide, V
yields a compound W, which is sparingly soluble in water.

When W reacts with hot acidified potassium dichromate, compound X was formed, which
gives an orange precipitate with 2,4-dinitrophenylhydrazine. X produces a silver mirror
upon reaction with Tollen’s reagent, but does not give any precipitate when heated with
Fehling’s solution. X also gives a yellow precipitate with a characteristic smell when heated
with alkaline aqueous iodine.

However, when W reacts with hot acidified potassium manganate (VII), compound Y is
produced. Y readily dissolves in sodium hydroxide and is isomeric with benzene-1,4-
dicarboxylic acid. Strong heating of Y under certain conditions causes each molecule of Y
to lose one water molecule to form the structure below.

Deduce the structures of compounds U to Y, explaining your reasoning.

9 Various hormones are involved in the regulation of the developmental transition stages of
insects. One such hormone, Precor, has the molecular formula C19H34O3. The following
partial structure of Precor is known:

CH3 CH3

H3C

CH3
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In refluxing Precor with dilute H2SO4, two compounds, S, C16H28O3, and T, C3H8O, are
formed. T gives a yellow precipitate when warmed with alkaline aqueous iodine. On heating
with acidified KMnO4, one mole of S forms one mole of U, C11H22O3, one mole of V, C3H4O,
and 2 moles of colourless gas X, which is non-polar but capable of permanent dipole-dipole
interaction when its molecules are in the correct orientation and in the solid state. X
undergoes hydrolysis to form a weak acid. U reacts with T when refluxed under acidic
conditions to form W, C14H28O3.

(a) Draw the structures of Precor, S, T, U, V, W and X.

(b) Write all relevant balanced equations and explain all chemical reactions involved.

(c) Draw the mechanism for the reaction of Precor to produce S and T.

(d) Draw the mechanism for the hydrolysis of X.

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11 Ammonia is manufactured by direct synthesis in the Haber Process:

N2(g) + 3H2(g) ⇌ 2NH3(g) ΔH = –92 kJ mol–1

(a) Write an expression for the equilibrium constant, Kc, for this reaction and give its units.

(b) When 3 mol of hydrogen and 1 mol of nitrogen were allowed to reach equilibrium in a
vessel of 1 dm3 capacity at 500°C and 1000 atm pressure, the equilibrium mixture
contained 0.27 mol of N2, 0.81 mol of H2 and 1.46 mol of NH3.

Calculate Kc at this temperature.

(c) Predict and explain the effect of an increase in temperature on:

(i) the value of Kc;

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(ii) the rate of the forward reaction.

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(d) When ammonium salts are dissolved in water, the following reaction occurs.

NH4+ (aq) + H2O(l) ⇌ NH3(aq) + H3O+ (aq)

(i) Write an expression for the dissociation constant, Ka, for NH4+ (aq).
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(ii) Calculate the pH of a solution of ammonium chloride of concentration 0.100 mol dm –3 at

298 K, the Ka value for NH4+ being 5.62 × 10–10 mol dm–3 at this temperature.

A2 Chemistry Equilibria Q12, 13

12 This question concerns acid-base equilibria.

(a)(i) Calculate the concentration, in mol dm–3, of a solution of hydrochloric acid, HCl, which has
a pH of 1.13.

(ii) Calculate the concentration, in mol dm–3, of a solution of chloric(l) acid, HOCl, which has a
pH of 4.23. Chloric(l) acid is a weak acid with Ka = 3.72 × 10–8 mol dm–3.
(b) The pH of 0.100 mol dm–3 sulphuric acid is 0.98.

(i) Calculate the concentration of hydrogen ions, H+, in this solution.

(ii) Write equations to show the two successive ionisations of sulphuric acid, H2SO4, in water.

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(iii) Suggest why the concentration of hydrogen ions is not 0.20 mol dm–3 in 0.100 mol dm–3
sulphuric acid.

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(c) Many industrial organic reactions produce hydrogen chloride as an additional product. This
can be oxidised to chlorine by the Deacon process:

4HCl(g) + O2(g) ⇌ 2Cl2(g) + 2H2O(g) ΔH = –115 kJ mol–1.

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0.800 mol of hydrogen chloride was mixed with 0.200 mol of oxygen in a vessel of volume
10.0 dm3 in the presence of a copper(I) chloride catalyst at 400 ºC. At equilibrium it was
found that the mixture contained 0.200 mol of hydrogen chloride.

(i) Write an expression for the equilibrium constant Kc.

(ii) Calculate the value of Kc at 400 ºC.

(d) State and explain the effect, if any, on the position of equilibrium in (c) of:

(i) decreasing the temperature;

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(ii) decreasing the volume;

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(iii) removing the catalyst.

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A2 Chemistry

13 Integrated circuits or ‘silicon chips’ are tiny electronic circuits produced within and upon a
single crystal of silicon. Most of the stages of chip manufacture involve chemical reactions
many of which are ultraclean chemical processes.

(a) The starting point in chip manufacture is silicon wafers – thin, polished slices of a single
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crystal of silicon. Silicon chips must be coated with a protective film – usually silicon(IV)
oxide (SiO2) but sometimes silicon nitride (Si3N4)

(i) Account for the difference in electrical conductivity among silicon, diamond and graphite.
Explain your answer.

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(ii) Suggest a reason why the name silicon(IV) oxide is preferable to silicon dioxide.

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(iii) Which sample will have a greater percentage by mass of silicon: 5.5 g of silicon nitride or
6.1 g of silicon (IV) oxide? Show your working clearly.

(b) Standard Clean 1 (SC1) is an aqueous cleaning agent used to remove microscopic
impurities from silicon chips during their manufacture. Organic contaminants can be
removed by an extremely powerful oxidising mixture called piranha solution, named for its
violent reaction with skin. It is formed by mixing pure sulphuric acid with 30% H2O2 in
approximately a 4:1 ratio. Peroxomonosulphuric acid or Caro’s acid, H2SO5, is believed to
be formed in high yield.

(i) Draw the displayed formula for Caro’s acid.

(ii) State the oxidation numbers of the sulphur atoms in sulphuric and Caro’s acid. Hence,
state, if any, the reaction undergone when sulphuric acid is converted to Caro’s acid.

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(iii) Write balanced half-equations showing the conversion of sulphuric acid to Caro’s acid and
hydrogen peroxide to water.

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(iv) Hence, write down the overall ionic equation showing the formation of Piranha solution.

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(c) Aluminium is used as a metal conductor on the surface of silicon chips due to its low
electrical resistance to maximise the speed at which electrical signals are passed.
However, aluminium suffers from electromigration – it diffuses into the underlying silicon
film when a voltage is applied across the chip.

The corrosion of aluminium in chips is also a potential problem since aluminium is highly
reactive to moist air, but luckily an oxide layer is formed almost instantaneously. This
coating prevents further reaction unless exposed to a corrosion catalyst like ‘chlorine’, as
shown in the equations below.

2Al(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2(g)

AlCl3(aq) + 3H2O(l) → Al(OH)3(s) + 3HCl(aq)

(i) Describe briefly what would happen if a few drops of a strong alkali are added to the
aluminium connections of a silicon chip.

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(ii) Explain why it is valid to mention that hydrogen chloride (‘chlorine’) acts as a corrosion
catalyst for aluminium.

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(iii) Corrosion of aluminium can also be caused by virtually every anion including carbonate,
nitrate, sulphate and fluoride.

State the electronic feature shared by sulphate, carbonate and nitrate ions, but not by
fluoride ions, explaining your reasoning by drawing appropriate structures.

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Chemistry Notes and Questions Chapter 20

14 The type of bonding between two elements can be rationalised and even
predicted using a van Arkel triangle. The triangle is based on electronegativity
values. Difference in electronegativity is plotted along the y-axis and average
electronegativity is plotted along the x-axis.
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(a) What is meant by the term electronegativity?

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(b) State and explain the trend in electronegativity

(i) across a period from left to right,

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(ii) down a group.

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(c) Use the electronegativity values quoted below to plot on the template van Arkel
triangle below each of the following compounds. Label your points with the
formulae.

(i) titanium boride, TiB2

(ii) silicon carbide, SiC
(iii) gallium antimonide, GaSb

(d) What is the type of bonding present at each of these bonding extremes,
labelled A, B and C on the triangle?
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A .......................................................

B .......................................................

C .......................................................

Cambridge Pre-U Specimen Paper

15 Ethyl ethanoate may be hydrolysed by treatment with aqueous sodium
hydroxide.

(a) Write an equation for this reaction, using structural formulae.

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(b) The rate equation for the reaction is found to be first order with respect to both
the concentration of hydroxide ion and the concentration of the ester.

(i) Write down the rate equation for the reaction, where the rate constant is k2.

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(ii) State the units of the rate constant k2.

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During the reaction, the concentrations of both the hydroxide ion and the ester
change. However, if the initial concentration of the ester, [ester]0, is much
larger than that of the hydroxide ion, the concentration of the ester remains
essentially constant as the hydroxide ion is used up during the reaction. The
reaction is then said to follow pseudo-first order kinetics.

rate of reaction = k1 [OH–]

where k1 is the pseudo-first order rate constant and k1 = k2 [ester]

In a typical experiment, 10.0 cm3 of 0.5 mol dm–3 aqueous ethyl ethanoate was
added to 10 cm3 of 0.005 mol dm–3 NaOH, all solutions being maintained at 0 °C.
The change in concentration of the hydroxide ion over the course of the
reaction was followed by monitoring the change in conductivity of the solution.
The data obtained is shown in the table.

(c)(i) From the data given in the table, calculate suitable values to enable you to plot
a graph to obtain the pseudo-first order rate constant, k1. Enter your values in
the blank column of the table. (A useful equation is provided in the Data
Booklet.)
(ii) By plotting a suitable graph on the grid below, determine the pseudo-first order
 18

rate constant, k1.

k1 = ...........................................

(iii) What is the concentration of ester at time t = 0?

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(iv) Hence, calculate the value of the second order rate constant, k2.
 19

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(v) How would you expect the gradient of your graph to change if the initial
concentration of the ester was doubled?

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End of Paper