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Section A
1 (a) Describe the thermal decomposition of the hydrogen halides HCl, HBr and HI
and explain any variation in their thermal stabilities. [3]
2HBr H2 + Br2
2HI H2 + I2
(b) Table 1.1 gives the melting points, in C, of the fluorides and chlorides of the
two elements in Period 3.
Table 1.1
magnesium silicon
fluoride 1261 90
chloride 714 70
Both MgF2 and MgCl2 are ionic compounds consisting of Mg2+ and X
held by strong ionic bonds between oppositely charged ions in a giant
ionic lattice. The lattice energy (strength of ionic bonds) is directly
proportional to the product of the cation and anion charges and
inversely proportional to the sum of the cationic and anionic radii. As
Cl is larger than F (one more quantum shell), the sum of the cationic
and anionic radii is larger for MgCl2 than for MgF2, hence the ionic
bonds are stronger in MgF2 than in MgCl2. More energy is required to
overcome the stronger ionic bonds in MgF2 than in MgCl2, hence
MgF2 has a higher melting point than MgCl2.
The halogens form many interhalogen compounds such as ClF3 and BrCl.
(c) The central atom in ClF3 is surrounded by five pairs of electrons arranged in a
trigonal bipyramidal shape. A trigonal bipyramidal arrangement is shown in Fig.
1.1.
Fig. 1.1
(Credit: http://www.chemguide.co.uk/atoms/bonding/shapesclf3.gif)
(ii) Apply the principles of the VSEPR theory to discuss the relative
stabilities of these three possible arrangements. [2]
VSEPR theory states that lone pair-lone pair repulsion is greater than
lone pair-bond pair repulsion, which in turn is greater than bond pair-
bond pair repulsion. The more stable arrangement should be such
that lone pair-lone pair/lone pair-bond pair/bond pair-bond pair
repulsions are minimised (i.e. oriented as far as possible).
If there are more than 4 electron pairs arranged around the central
atom, repulsions at angles greater than 90 can be neglected.
(d) When benzene is heated with BrCl and AlCl3, a monohalogenobenzene, C6H5X,
is formed.
(ii) Draw the mechanism of the reaction, showing any intermediates. [2]
Electrophilic substitution
Cl Cl
+ +
Br Cl Br + Cl Al Cl
Al
Cl Cl Cl
H
+ Br
Br slow
+
H :Cl
Br
Br Cl Al Cl fast
+ + HCl + AlCl3
Cl
(i) Write the expression for the solubility product, Ksp, of silver chloride,
stating its units. [1]
(ii) An excess of solid silver chloride was stirred with 0.50 mol dm3 AgNO3
until equilibrium was established.
Calculate [Cl(aq)] in the resulting solution, given the value of Ksp is 2.0
1010. [1]
adding NH3(aq),
adding NaCl(aq). [2]
[Total: 18]
2 There are over 20 different binary compounds containing only the elements nitrogen
and hydrogen. The most common of these is ammonia, but others include hydrazine,
diazene, and hydrogen azide. Their formulae are shown in Table 2.1.
Table 2.1
molecular
compound
formula
ammonia NH3
hydrazine N2H4
diazene N2H2
(a) (i) Hydrazine has a boiling point of 114C and ammonia has a boiling point
of 33C.
(ii) Write an equation for the reaction between hydrazine and sulfuric acid,
identifying the conjugate acid-base pairs in the reaction. [2]
(b) There are two isomers of diazene which can be isolated at low temperatures.
Suggest a structure for diazene, using the usual valencies of hydrogen and
nitrogen. Predict its bond angles and explain how the two isomers arise. [3]
HN=NH
Each nitrogen atom has two bond pairs and one lone pair, i.e. V-shaped,
bond angle <120
H
.. .. ..
N N
.. N N
H H H
trans-diazene cis-diazene
Moist red litmus paper held at the mouth of the tube turns blue.
Suggest the formulae of the particles in the gaseous mixture formed when solid
A sublimes and in a solution of A in water. [3]
(d) Sodium azide, NaN3, is used in some airbags. When NaN3 is ignited, it
undergoes rapid decomposition into nitrogen gas and sodium metal. All the
sodium is then removed by reaction with an excess of sodium nitrate, NaNO 3,
in the airbag. This produces sodium oxide, Na2O, and more nitrogen gas.
(i) Construct a balanced equation for the overall process forming Na2O
and N2 from NaN3 and NaNO3 in the airbag. [1]
(e) Hydrogen azide is used as a reagent in the Schmidt reaction, which inserts an
NH group into the CC bond adjacent to a carbonyl group.
(i) Name the functional group that is formed during this reaction. [1]
Secondary amide
O
step 1 step 2 NH O
C
+HN3
+
B N
O O
D
Fig. 2.1
(ii) Suggest a structure for intermediate C, and reagents and conditions for
step 1. [2]
+
N
O O C
Compound B can be made from benzene by the synthesis shown in Fig. 2.2.
Cl O
Fig. 2.2
(iii) Suggest reagents and conditions for step 3 and for step 4. [2]
(iv) Suggest reagents and conditions for step 5, and the structure of
intermediate E. [2]
OH
NH O NH2
+ +
N N
O O O O
D F
Fig. 2.3
NaOH(aq), heat
(vi) Describe and explain how the basicity of D would compare to that of F.
[2]
[Total: 23]
3 (a) State two chemical or physical properties of copper, apart from the colour of
the metal, in which it differs from calcium.
Copper can exhibit multiple oxidation states, 0, +1 and +2, whereas calcium
can only exhibit two oxidation states, 0 and +2. This is because the 4s orbital
and 3d orbital in copper have very similar energies and there is not a huge
jump in the amount of energy in removing a second electron compared with
the first in forming Cu2+ from Cu+. However, for calcium, there is a significant
jump in the amount of energy in removing a third electron compared with the
second in forming Ca3+ from Ca2+, hence this is not energetically feasible.
Copper has higher melting and boiling points than calcium because of
stronger metallic bonding in copper as both 4s and 3d electrons are
delocalised into the sea of electrons and involved in the metallic bonding due
to similar energies of 4s orbitals and 3d orbitals; whereas only the 4s
electrons are involved in metallic bonding in the case of calcium.
(b) Aqueous copper(II) ions, Cu2+(aq), are blue, whereas aqueous zinc(II) ions,
Zn2+(aq), are colourless.
(i) Explain why Cu2+(aq) are coloured, whereas Zn2+(aq) ions are not. [4]
When ligands bond with a transition metal ion, repulsion between the
electrons in the ligands and electrons in the d orbitals of the transition
metal ion raises the energy of the d orbitals, causing the d orbitals to
split into two groups, one group with higher energy and the other
group with lower energy. When light passes through a solution of the
transition metal ion, some of the light is used to promote an electron
from the lower energy set of orbitals to the higher energy set of
orbitals. This is known as d-d transition. The particular wavelength
which corresponds to the energy gap is absorbed, and the
complementary colour is observed.
(ii) Explain the meaning of the terms ligand and complex, using the reaction
between Cu2+(aq) ions and ammonia to illustrate your answer. [3]
(c) An acidified solution, G, of a vanadium compound was divided into two portions.
A 25.0 cm3 sample of one portion required 16.4 cm3 of 2.00 103 mol dm3
KMnO4 solution for complete oxidation of the compound to the
dioxovanadium(V) ion, VO2+(aq).
A 25.0 cm3 sample of solution H required 24.6 cm3 of 2.00 103 mol dm3
KMnO4 for complete oxidation to the dioxovanadium(V) ion, VO2+(aq).
(d) Compound I, C6H8O2, decolourises bromine water, but does not react with
sodium metal or alkaline aqueous iodine. A solution of I is optically active.
When heated with H2SO4(aq) it forms J, C6H10O3, which on heating with
acidified KMnO4 produces K, C3H4O3, as the only product. K reacts with
sodium metal and also with alkaline aqueous iodine.
Suggest structures for I, J and K and explain the reactions described. [7]
Compound I
Decolourises bromine water electrophilic addition of alkene or electrophilic
substitution of phenol
Does not react with sodium metal or alkaline aqueous iodine not alcohol,
phenol, acid, methyl alcohol, methyl ketone
Compound J
J is a hydrolysis product, i.e. secondary alcohol and carboxylic acid
Reacts with KMnO4 to produce K oxidative cleavage of alkene; oxidation
of secondary alcohol to ketone
Compound K
Reacts with sodium metal acid-metal (redox) reaction of carboxylic acid
or tertiary alcohol (cannot be primary or secondary alcohol due to oxidation
with KMnO4)
Reacts with alkaline aqueous iodine triiodomethane reaction of methyl
ketone
* O OH
OH O OH
O
I O J O K
[Total: 19]
Section B
4 (a) World supplies of methane (natural gas) are diminishing. Methods are being
developed to produce methanol from the anaerobic fermentation of waste
organic matter.
oxidation number of H = 1
oxidation number of O = 2
average oxidation number of C = x
oxidation number of butanoic acid = sum of oxidation numbers
4x + 8(1) + 2(2) = 0
4x = 4
x = 1
(iii) Suggest a method for removing the CO2 from the gaseous product
mixture in (a)(ii). [1]
(iv) A sample of the gaseous product mixture from the complete reaction in
(a)(ii), at an initial pressure of 1.5 105 Pa, had all of its CO2 removed.
(b) Some relevant standard enthalpy change of formation values, Hf, are given
in Table 4.1.
Table 4.1
CH3CH2CH2CO2H 534
H2O 286
CH4 75
CO2 394
(i) Calculate the enthalpy change, Hr, for the reaction represented by
your equation in (a)(ii), using the data in Table 4.1. [2]
(ii) The value of Gr at 298 K for the same reaction is 207 kJ mol1.
Calculate Sr for the reaction, and explain its sign with reference to
your equation in (a)(ii). [2]
G = H TS
207 = +41.5 (298)S
S = 834 J K1 mol1
(i) Outline the mechanism of the reaction between methane and bromine
to form bromomethane. [4]
(ii) Use your mechanism to explain why the bromination of methane can
be carried out with light of a longer wavelength (yellow light is adequate)
than that needed for the chlorination of methane (blue or ultraviolet light
is required). [1]
+ +
Cl
3-ethylpentane Cl
Cl
L M N
Fig. 4.1
Only one hydrogen atom (the one bonded to the central carbon) can
be substituted to produce L.
(iv) When the chlorination is carried out and the products are analysed, it is
found that the mole ratio of L : N formed is about 2 : 1.
Suggest an explanation for the difference between this ratio and the
one you gave in (c)(iii). [2]
Fig. 4.2
Q: CH3CH2CHClCO2H
R: CH3CH2CH(NHCH2CH3)CO2H
S: CH3CH2CH(NHCH2CH3)CH2OH
[Total: 20]
5 (a) Describe reactions that illustrate the variation in acid-base behaviour of the
oxides of elements in Period 3 (sodium to sulfur), using at least three oxides as
examples.
(b) Chlorine dioxide, ClO2, is a yellow gas. Although it is unstable and explosive
when pure, it is an important commercial chemical. Over a million tonnes are
produced annually for use in the bleaching of wood pulp for paper-making and
the sterilisation of water supplies.
(i) State the changes in oxidation numbers that occur during this reaction
and use them to construct the balanced equation for the reaction. [2]
(ii) Construct a suitable energy cycle using this equation and use data from
the Data Booklet and your cycle to calculate the Cl=O bond energy in
ClO2. [2]
(iii) Explain how the value and sign of G would compare to the value and
sign of H for the decomposition of ClO2. [2]
(c) The following scheme shows a synthesis of the beta-blocker drug, metoprolol.
Study Fig. 5.1 carefully and answer the questions that follow.
OH OH OH OH
ClCOCH3Cl CH3ONa H2 + Pd
step 1 step 2 step 3
Cl O O
O O
NaOH step 4
O N +
O Br O O Na
H
OH OH
+U +T
Br2(aq)
step 7 step 6 step 5
O O O O
Fig. 5.1
(i) State the types of reaction that occur during each of the steps 3 and 4.
[2]
Step 3: reduction/hydrogenation
Step 4: acid-base reaction
(ii) Name the mechanism of the reaction in each of the steps 1, 2 and 6.
[3]
CH2ClCH=CH2
NH2CH(CH3)2
(v) Explain why step 6 forms the isomer shown in Fig. 5.1 and not the
isomer shown in Fig. 5.2. [1]
O OH
Br
Fig. 5.2
[Total: 20]