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2017 H2 Chemistry Paper 3

Section A

Answer all the questions in this section.

1 (a) Describe the thermal decomposition of the hydrogen halides HCl, HBr and HI
and explain any variation in their thermal stabilities. [3]

Hydrogen halides undergo thermal decomposition to form hydrogen gas and


their corresponding halogens (as reddish-brown fumes in the case of Br2 and
dark purple fumes for I2) as the only products:

2HBr H2 + Br2
2HI H2 + I2

HCl is thermally stable and does not decompose on heating.

The thermal stabilities of hydrogen halides decrease in the following order:


HCl (most thermally stable), HBr and HI (least thermally stable). This is due
to the increase in bond length. As a result, the effectiveness of orbital overlap
and hence bond energy decreases from HCl to HBr to HI. As such, the
energy required to break the HX bond decreases from HCl to HBr to HI
(hence thermal stabilities decrease from HCl to HBr to HI).

(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

Explain, in terms of structure and bonding, the differences in melting point


between

(i) MgCl2 and SiCl4, [2]

MgCl2 is an ionic compound. It consists of Mg2+ and Cl held by strong


ionic bonds between oppositely charged ions in a giant ionic lattice
structure, which require a lot of energy to overcome during melting.
Hence, MgCl2 has a high melting point.

SiCl4 is a covalent compound. It exists as simple covalent molecules


of SiCl4 held together by weak van der Waals forces of attraction
between the discrete molecules, which require little energy to
overcome during melting. Hence, SiCl4 has a low melting point.

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

(ii) SiF4 and SiCl4, [1]

Both SiF4 and SiCl4 are covalent compounds existing as simple


covalent molecules held together by weak van der Waals forces of
attraction. As SiCl4 has a larger electron cloud size than SiF4, the
electron cloud of SiCl4 is more polarisable than that of SiF4, resulting
in stronger van der Waals forces in SiCl4 than in SiF4. More energy
is required to overcome the stronger van der Waals forces in SiCl 4
than in SiF4, hence SiCl4 has a higher melting point than SiF4.

(iii) MgF2 and MgCl2. [1]

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

Three different molecular arrangements of ClF3 are possible.

(i) Draw clear diagrams of these three molecular arrangements, each


showing the five pairs of electrons. State which arrangement, if any,
would result in a molecule with no dipole moment. [2]

Arrangement 1: 2 lone pairs occupying axial positions


Arrangement 2: 2 lone pairs occupying equatorial positions
Arrangement 3: 1 lone pair occupying equatorial position; 1 lone pair
occupying axial position

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2017 H2 Chemistry Paper 3

(Credit: http://www.chemguide.co.uk/atoms/bonding/shapesclf3.gif)

Arrangement 1 would result in a molecule with no dipole moment


(lone pairs occupying axial positions are linearly arranged with
respect to each other, hence cancelling dipole moment; halogen
atoms occupying equatorial positions are arranged in a trigonal
planar manner with respect to each other, hence cancelling dipole
moment).

(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.

In arrangement 3, two lone pairs are at 90 to each other, whereas in


the other two arrangements, they are at more than 90 to each other
and can be neglected (arrangement 1: 180, arrangement 2: 120).
Hence, arrangement 3 is the least stable with the greatest amount of
repulsion.

In arrangement 1, each lone pair is at 90 to 3 bond pairs. Given two


lone pairs, there are a total of six lone pair-bond pair repulsions.
(Bond pair-bond pair repulsions can be neglected as they are at 120
to each other.)

In arrangement 2, each lone pair is at 90 to 2 bond pairs. Given two


lone pairs, there are a total of four lone pair-bond pair repulsions.
(Each lone pair is 120 to one equatorial fluorine atom and to each
other, which can be neglected.) The equatorial bond pair is at 90 to
each axial bond pair above and below the plane, hence there are two
bond pair-bond pair repulsions.

Since lone pair-bond pair repulsion is greater than bond pair-bond


pair repulsion, arrangement 2 has the least repulsions and is the most
stable.

(d) When benzene is heated with BrCl and AlCl3, a monohalogenobenzene, C6H5X,
is formed.

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

(i) Suggest whether the product C6H5X is chlorobenzene or


bromobenzene. Give a reason for your answer. [1]

Bromobenzene. As chlorine is more electronegative than bromine, Br


bears a partial positive charge in BrCl, hence acting as the
electrophile involved in the electrophilic substitution reaction.

(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

(e) Silver chloride is sparingly soluble in water

AgCl (s) Ag+(aq) + Cl(aq)

(i) Write the expression for the solubility product, Ksp, of silver chloride,
stating its units. [1]

Ksp = [Ag+(aq)][Cl(aq)] units: mol2 dm6

(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]

[Ag+(aq)] = [Ag+(aq)] from AgNO3 + [Ag+(aq)] from AgCl


[Ag+(aq)] from AgNO3 (AgCl is sparingly soluble)
= 0.50 mol dm3

Hence, [Cl(aq)] = Ksp / [Ag+(aq)] 2.0 1010 / 0.50


= 4.0 1010 mol dm3

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

(iii) Describe and explain how the solubility of AgCl is affected by

adding NH3(aq),
adding NaCl(aq). [2]

When NH3(aq) is added, a ligand exchange reaction takes place


between Ag+(aq) and NH3(aq) to form the complex Ag(NH3)2+(aq).
This decreases [Ag+(aq)] and causes the position of equilibrium to
shift to the right, hence increasing solubility of AgCl.

When NaCl(aq) is added, [Cl(aq)] increases, causing the position of


equilibrium to shift to the left, hence decreasing solubility of AgCl due
to common ion effect.

[Total: 18]

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

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

hydrogen azide HN3

(a) (i) Hydrazine has a boiling point of 114C and ammonia has a boiling point
of 33C.

Suggest a reason for the high boiling point of hydrazine compared to


ammonia. [1]

Hydrazine has a more extensive intermolecular hydrogen bonding


than ammonia. On average, each hydrazine molecule can form two
hydrogen bonds with neighbouring hydrazine molecules; whereas
each ammonia molecule can only form one hydrogen bond with a
neighbouring ammonia molecule. Hence, more energy is required to
overcome the more extensive hydrogen bonding in hydrazine,
resulting in higher boiling point compared to ammonia.

(ii) Write an equation for the reaction between hydrazine and sulfuric acid,
identifying the conjugate acid-base pairs in the reaction. [2]

N2H4 + H2SO4 N2H5+ + HSO4


base acid conjugate acid conjugate base

(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

Diazene can exhibit geometric (cis-trans) isomerism, due to the presence of


a double bond between the two nitrogen atoms (restricted rotation), and two
different groups bonded to each nitrogen atom (a hydrogen atom and a lone
pair).

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

H
.. .. ..
N N
.. N N

H H H
trans-diazene cis-diazene

(c) When ammonia is bubbled through a sample of hydrogen azide dissolved in an


organic solvent, white crystals of compound A, N4H4, are precipitated.

Heating solid A to 133C in a test-tube causes it to sublime.

Moist red litmus paper held at the mouth of the tube turns blue.

A solution of A in water is a good conductor of electricity.

Suggest the formulae of the particles in the gaseous mixture formed when solid
A sublimes and in a solution of A in water. [3]

Sublimation: N4H4(s) NH3(g) + HN3(g)


turns moist red litmus paper blue

Dissolution: N4H4(aq) NH4+(aq) + N3(aq)

(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]

5NaN3 + NaNO3 3Na2O + 8N2

(ii) When 400 g of NaN3 is ignited, it inflates an empty airbag to a volume


of 100 dm3. Calculate the final pressure in the airbag, at a temperature
of 298 K. [3]

No. of moles of NaN3 = 400 / (23 + 3 14) = 6.1539 mol


No. of moles of N2 = 8/5 6.1539 = 9.8462 mol
pV = nRT
p = nRT/V = (9.8462)(8.314)(298)/(100 103) = 2.44 105 Pa

(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.

RCOR + HN3 RNHCOR + N2

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

(i) Name the functional group that is formed during this reaction. [1]

Secondary amide

The 2-stage synthesis of compound D from compound B, shown in Fig. 2.1,


makes use of this reaction.

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

Step 1: concentrated nitric acid, concentrated sulfuric acid, heat

Compound B can be made from benzene by the synthesis shown in Fig. 2.2.

Cl O

step 3 step 4 step 5 step 6


E
heat with
K2Cr2O7 + B
dil. H2SO4

Fig. 2.2

(iii) Suggest reagents and conditions for step 3 and for step 4. [2]

Step 3: CH3CH2Cl, AlCl3, heat


Step 4: limited Cl2(g), ultraviolet light

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

(iv) Suggest reagents and conditions for step 5, and the structure of
intermediate E. [2]

Step 5: NaOH(aq), heat

OH

Compound D can be converted into compound F.

NH O NH2

+ +
N N
O O O O
D F

Fig. 2.3

(v) Suggest reagents and conditions for this reaction. [1]

NaOH(aq), heat

(vi) Describe and explain how the basicity of D would compare to that of F.
[2]

D is neutral whereas F is basic. This is because the phenylamine


functional group in F has a lone pair available for donation in an acid-
base reaction. However, the lone pair on the nitrogen atom in the
amide group of D is resonance-stabilised in the amide bond, making
it less available for donation in an acid-base reaction.

[Total: 23]

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

3 (a) State two chemical or physical properties of copper, apart from the colour of
the metal, in which it differs from calcium.

Explain the reasons for those differences. [2]

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.

Cu2+(aq) has partially filled 3d orbitals, hence d-d transition is


possible, resulting in a coloured solution. However, Zn2+(aq) has
completely filled 3d orbitals, making d-d transition impossible, hence
resulting in a colourless solution.

(ii) Explain the meaning of the terms ligand and complex, using the reaction
between Cu2+(aq) ions and ammonia to illustrate your answer. [3]

In the reaction between Cu2+(aq) and ammonia, ammonia acts as a


ligand (i.e. a species with at least one lone pair of electrons to form a
coordinate bond with the central metal ion) and undergoes a ligand-
exchange reaction with Cu2+(aq) as follows:

[Cu(H2O)6]2+(aq) + 4NH3(aq) [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

The resultant [Cu(NH3)4(H2O)2]2+(aq) is a complex, i.e. a metal ion at


its centre with a number of other molecules/ions (ligands)
surrounding it.

(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).

An excess of powdered zinc, E (Zn2+/Zn) = 0.76 V, was added to the other


portion of G. The mixture was stirred until the reaction was complete, and then
filtered. The filtrate was solution H.

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).

Deduce the oxidation states of vanadium in solution G and in solution H, and


hence calculate the concentration of vanadium ions in solution G. [3]

1st portion (oxidation from higher oxidation state to +5):


No. of moles of MnO4 required = 16.4/1000 2.00 103 = 3.28 105 mol
No. of moles of e involved in redox = 5 3.28 105 = 1.64 104 mol

2nd portion (oxidation from lower oxidation state to +5):


No. of moles of MnO4 required = 24.6/1000 2.00 103 = 4.92 105 mol
No. of moles of e involved in redox = 5 4.92 105 = 2.46 104 mol

Ratio of no. of moles of e in 1st portion to 2nd portion = 2 : 3


Hence, it can be deduced that oxidation state in G is +3 and oxidation state
in H is +2.

No. of moles of vanadium ions in 25.0 cm3 of solution G


= 1.64 104 / 2 = 0.82 104 mol

Concentration of vanadium ions in solution G


= 0.82 104 / 0.0250 = 3.28 103 mol dm3

(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

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

Heated with H2SO4(aq) molecular formula increases by +H2O, i.e.


hydrolysis of ester, since only one hydrolysis product, I is a cyclic ester
Optically active presence of chiral carbon (marked with *)

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]

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

Section B

Answer one question from this section.

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.

The fermenting bacteria gain energy by metabolising organic compounds


through a series of disproportionation reactions, which form methane, CH4, and
carbon dioxide, CO2, only.

(i) Calculate the average oxidation number of carbon in butanoic acid,


CH3CH2CH2CO2H. [1]

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

(ii) Construct a balanced equation for the disproportionation reaction of


aqueous butanoic acid, CH3CH2CH2CO2H, to produce CH4 and CO2
only, by using oxidation numbers or otherwise. [1]

[R] CH3CH2CH2CO2H + 12H+ + 12e 4CH4 + 2H2O 2.5


[O] CH3CH2CH2CO2H + 6H2O 4CO2 + 20H+ + 20e 1.5
Overall: CH3CH2CH2CO2H + H2O 2.5CH4 + 1.5CO2

(iii) Suggest a method for removing the CO2 from the gaseous product
mixture in (a)(ii). [1]

Bubble the gaseous product through sodium hydroxide solution.

(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.

Calculate the pressure of the remaining methane, assuming the


temperature and volume remain constant. [1]

At constant temperature and volume, p is directly proportional to n


pressure of remaining methane = 5/8 1.5 105 = 9.38 104 Pa

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

(b) Some relevant standard enthalpy change of formation values, Hf, are given
in Table 4.1.

Table 4.1

compound Hf/kJ mol1

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]

Hr = 2.5(75) + 1.5(394) (534) (286) = +41.5 kJ mol1

(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

The sign of the entropy change of reaction is positive due to increase


in the number of moles of gaseous products (from 0 to 4 mol) and
hence an increase in disorder and the number of ways energy can
be distributed.

(c) Light of a longer wavelength is lower in energy than light of a shorter


wavelength. Chlorine and bromine react with alkanes in the presence of light.

(i) Outline the mechanism of the reaction between methane and bromine
to form bromomethane. [4]

Free radical substitution


Initiation: Br2 2Br
Propagation:
CH4 + Br CH3 + HBr
CH3 + Br2 CH3Br + Br
Termination:
CH3 + Br CH3Br
2CH3 CH3CH3
2Br Br2

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

(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]

In free radical substitution, the first step (initiation) involves the


homolytic fission of the XX bond. Since BrBr is longer than ClCl,
the orbital overlap is less effective and hence bond energy is weaker.
Thus, light of a longer wavelength (with lower energy) is sufficient to
break the bond to form the free radicals.

There are three possible monochloroalkanes that can be formed from 3-


ethylpentane.

+ +
Cl
3-ethylpentane Cl
Cl

L M N

Fig. 4.1

(iii) Predict the relative proportions of L, M and N that are likely to be


produced from 3-ethylpentane. Explain your answer. [2]

Only one hydrogen atom (the one bonded to the central carbon) can
be substituted to produce L.

Six hydrogen atoms (the ones bonded to the penultimate carbon in


each ethyl group CH2CH3) can be substituted to produce M.

Nine hydrogen atoms (the ones bonded to the terminal carbon in


each ethyl group CH2CH3) can be substituted to produce N.

Therefore, based on probability, the relative proportions of L, M and


N are 1 : 6 : 9.

(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]

The radical intermediate produced in the formation of L is a tertiary


radical, whereas the radical produced in the formation of N is a
primary radical.

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

A tertiary radical (an electron-poor species) is more stable than a


primary radical due to more electron-donating alkyl groups present (3
alkyl groups in tertiary radical versus 2 in primary radical).

Hence, the formation of the tertiary radical to produce L is more


thermodynamically favoured than the formation of the primary radical
carbocation to produce N.

(d) 2-chlorobutanoyl chloride, P, can be obtained from butanoic acid by heating it


with Cl2 and PCl5.

CH3CH2CH2CO2H + Cl2 + PCl5 CH3CH2CHClCOCl + HCl + POCl3

P can then be used to produce S, C6H15NO, via compounds Q and R, as shown


in Fig. 4.2.

NaOH(aq) CH3CH2NH2 LiAlH4


P Q R S
room temperature C6H15NO

Fig. 4.2

Suggest structures for compounds Q, R and S in Fig. 4.2. [3]

Q: CH3CH2CHClCO2H
R: CH3CH2CH(NHCH2CH3)CO2H
S: CH3CH2CH(NHCH2CH3)CH2OH

[Total: 20]

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

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.

Write equations for all reactions you describe. [6]

The variation in acid-base behaviour of the oxides of elements in Period 3


changes from basic oxide in sodium/magnesium to amphoteric oxide in
aluminium and to acidic oxide in silicon/phosphorus/sulfur.

Basic oxide (e.g. Na2O):


Na2O(s) + 2HCl(aq) 2NaCl(aq) + H2O(l)

Amphoteric oxide (e.g. Al2O3):


Al2O3(s) + HCl AlCl3(aq) + H2O(l)
Al2O3(s) + 2NaOH + 3H2O 2NaAl(OH)4(aq)

Acidic oxide (e.g. SO2):


SO2(g) + 2NaOH(aq) Na2SO3(aq) + H2O(l)

(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.

It can be made in the laboratory by the action of concentrated sulfuric acid on


potassium chlorate(V), KClO3. In addition to ClO2, the products of the reaction
include KClO4, KHSO4 and H2O.

(i) State the changes in oxidation numbers that occur during this reaction
and use them to construct the balanced equation for the reaction. [2]

The oxidation number of Cl decreases from +5 in KClO3 to +4 in ClO2.

The oxidation number of Cl increases from +5 in KClO3 to +7 in


KClO4.

[R] ClO3 + 2H+ + e ClO2 + H2O


[O] ClO3 + H2O ClO4 + 2H+ + 2e

3KClO3 + 2H2SO4 2ClO2 + KClO4 + 2KHSO4 + H2O

Chlorine dioxide readily decomposes to its elements.

2 O=Cl=O(g) Cl2(g) + 2O2(g) H = 204 kJ mol1

(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]

BE(ClCl) = 244 kJ mol1


BE(O=O) = 496 kJ mol1

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

H = 4BE(Cl=O) 244 2(496) = 204 kJ mol1


BE(Cl=O) = +258 kJ mol1

(iii) Explain how the value and sign of G would compare to the value and
sign of H for the decomposition of ClO2. [2]

The sign of the entropy change for the decomposition of ClO2 is


positive due to an increase in the number of moles of gaseous
products in the reaction from 2 moles to 3 moles, leading to an
increase in disorder and the number of ways energy can be
distributed.

Since G = H TS, and H is negative, G is negative for all


temperatures (assuming H is negative for all temperatures).

Hence, the absolute value (magnitude) of G is larger than that of


H.

(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]

Copyright 2017 by Lee Jun Hui


2017 H2 Chemistry Paper 3

Step 1: electrophilic substitution


Step 2: nucleophilic substitution, SN2
Step 6: electrophilic addition

(iii) Suggest the identity of the reagent T in step 5. [1]

CH2ClCH=CH2

(iv) Suggest the identity of the reagent U in step 7. [1]

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

The carbocation intermediate produced in the formation of the isomer


shown in Fig. 5.1 is secondary whereas that produced in the
formation of the isomer shown in Fig. 5.2 is primary.

A secondary carbocation is more stable due to the presence of one


more alkyl group which is electron-donating and disperses the
positive charge. Hence, the formation of the isomer shown in Fig. 5.1
is more thermodynamically favoured.

[Total: 20]

Copyright 2017 by Lee Jun Hui