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The document discusses chemistry concepts and techniques related to stoichiometry, atomic structure, periodicity, bonding, energetics and organic chemistry.

The main topics covered include stoichiometry, atomic structure, periodicity, bonding and organic chemistry. Concepts like moles, isotopes, ionization energy and structural isomers are discussed.

Techniques like thin layer chromatography, gas chromatography and high performance liquid chromatography are discussed for separating mixtures.



Answers to examination
questions in Chapters 1 to 21
4 a Amount of hydrochloric acid
13.95dm 3
=
2.00moldm3 = 0.0279mol
[1]
1000
b Amount of sodium carbonate in 20.00cm3 of
solution = 0.01395mol
[1]
c Concentration of sodium carbonate
1000 dm 3
=
0.01395mol = 0.6975mol
[1]
20
d Molar mass of hydrated sodium carbonate
200.00 g
= 286.74gmol1[1]
=
0.6975mol
e Molar mass of anhydrous sodium carbonate,
Na2CO3 = (22.99 2) + 12.01 + (3 16.00)
= 105.99gmol1

Molar mass of water = 286.74gmol1 105.99gmol1
= 180.75gmol1
180.75g mol 1
Hence, n =
= 10
[2]
18.02 g mol 1

1 Stoichiometric relationships
Paper 1
1 D

14 A

2 B

15 D

3 D

16 C

4 C

17 B

5 D

18 D

6 D

19 A

7 D

20 B

8 C

21 B

9 B

22 D

10 D

23 A

11 B

24 D

12 D

25 A

13 B

26 D

Paper 2
1 a C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)[2]

5 a 3Ag+(aq) + XO43 (aq) Ag3XO4(s)[1]


b i Amount of silver ions =
0.2040moldm3 0.04118dm3 = 8.401 103mol[1]
1
ii Amount of Ag3XO4 = 8.401 103 mol
3

= 2.800 103mol[1]
iii 2.800 103 mol of Ag3XO4 weighs 1.172g.
Hence one mole weighs
1.172 g

= 418.6gmol1 
2.800 103 mol

b Carbon dioxide produced = 20cm3


Oxygen remaining = 10cm3 [2]

2 a Zn(s) + I2(s) ZnI2(s)[1]


100g
= 1.530mol
b Amount of zinc =
65.37g mol 1
100g

Amount of iodine =

The reacting molar ratio is 1:1 therefore the zinc is


present in excess.
[3]

= 0.3940mol

c Amount of zinc iodide = amount of iodine used


100
Amount of zinc iodide =
= 0.3940mol
253.8

100
(65.37 + 253.8)
235.8
= 125.8g

Mass of zinc iodide =


3 a

253.8 g mol 1

V
V 1 V2 955cm 3
;
= 2 ; V2 = 1041cm3
=
303K
T1 T2 278K
The balloon will burst.

[1]

iv (3 107.87) + X + 4 (16.0) = 418.6;


hence X = 30.99 and X is phosphorus (P).
(1g)
6 11mg
= 0.0011g
(1000 mg)
mass of solute(g)
ppm =
106ppm
mass of solvent and solute(g)
0.011g
=
106ppm/1 = 5.5ppm
(2000 g + 0.011g)

b The increase in temperature increases the average


kinetic energy of the nitrogen molecules and hence
increases their average speed. They collide more
frequently and energetically with each other and
the walls of the balloon.
[2]

[2]

[2]

7 IO3 (aq) + 5I(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)


KIO
0.6125g
Amount of KIO3/IO33 =
= 0.00286mol
214.00 g
mol 1 in 250
IO 3
cm3

3
Amount of KIO3/IO3 in 25.00cm = 0.000286mol

[3]

[2]

Amount of I2 = 8.58 104mol

2 S2 O 32 (aq) + I2(aq) 2I(aq) + S 4 O 62 (aq)



Amount of S2 O 32 (aq) = 1.716 103mol in 24.50cm3


1000 1.716 103
Concentration of Na2S2O3 =
24.50

= 0.07moldm3

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

2 Atomic structure
Paper 1

electrons move from high energy levels to lower


energy levels. Light of a particular frequency is
released during this process.

[2]

5 a Weighted average mass of naturally occurring


1
isotopes of an element compared to g of
12
carbon-12. 

[1]

1 D

12 B

2 C

13 D

3 A

14 D

4 D

15 D

5 C

16 A

vaporization/vaporized sample;

6 D

17 A

ionization/electron gun;

7 C

18 B

acceleration/oppositely charged plates;

8 A

19 A

deflection/magnetic field;

9 C

20 D

detection

10 C

21 C

11 A

22 A

b Diagram of mass spectrometer containing in the


correct sequence:

[5]

c 63x + 65(1 x) = 63.55


Cu = 72.5% and 65Cu = 27.5%

[2]

d Cobalt-60 ( Co), iodine-131 ( I) or


iodine-125 (125I) 

[1]

63

60

Paper 2
1 a

An atom of 79Br

An ion of 81Br

Protons

35

35

Neutrons

44

46

Electrons

35

36

 [3]

131

3 Periodicity
Paper 1
1 A

13 C

[1]

2 D

14 A

2 a Atoms of the same element but with different mass


numbers and hence different number of neutrons. [1]

3 A

15 B

4 C

16 B

5 C

17 D

6 B

18 D

7 B

19 B

8 A

20 C

9 A

21 B

10 A

22 B

11 C

23 C

12 C

24 D

Br because its relative isotopic mass is closer


to 79.90.
79

b 47 protons, 46 electrons and 60 neutrons.

[2]

c Carbon-12 (12C).[1]
n=
n=6
n=5

n=4
A

n=3
B

n=2

Paper 2
1 a i

n=1

a Line starting at n = 1;

Line finishing at n = (not above );

Upward arrow

[2]

ii Al(g) Al+(g) + e[1]

[2]

b The magnesium atom has a greater nuclear charge


due a higher number of protons. Consequently,
the atomic radius is smaller and there is a stronger
attraction for the electrons by the nucleus.
[3]

b Line from n = 3 to n = 2;

Arrow pointing downward (in any transition)

4 The emission spectrum consist of a series of sharp or


discrete coloured lines on a black background. 
[1]

The lines converge together at high energy (high


frequency). The lines are generated when excited

The minimum energy required for the removal


of a mole of electrons from a mole of gaseous
atoms to form a mole of unipositive gaseous
ions. 
[2]

c 2Li(s) + 2H2O(l) 2LiOH(aq) + H2(g)

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015


There will be effervescence: release of gas at the
surface. Bubbles of a colourless gas will be observed.
The lithium moves around the surface and is
converted into a soluble product. Heat and sound
energy are released.
[3]

2 a i

The bromine atom has a greater number of


protons and hence a greater nuclear charge: 35+
versus 34+. Hence the outer or valence electrons
are attracted more strongly. The bromide ion is
formed by the addition of one electron to the
bromine atom; the selenide ion is formed by
the addition of two electrons to the selenium
atom. The additional electrons cause electron
electron repulsion which increase radii. The
effect is highest in the selenide ion.
[2]

ii The electronegativity is the ability of atom to


attract a bonding pair of electrons in a covalent
bond. Fluorine has a smaller radius and hence
the electrons are closer to a nucleus in a lower
energy level. The electrons are repelled by
fewer inner electrons and there is a decreased
shielding effect.
[3]

b i

Brown solution formed; Cl2 + 2KI I2 + 2KCl;


Cl2 + 2I I2 + 2Cl[2]

ii A cream or off-white precipitate (solid) is


formed: Ag+ + Br AgBr

[2]

c The reaction in (i) is redox. The chlorine is


reduced/gains electrons/decreases its oxidation
number. The iodide ion is oxidized/loses electrons/
increases its oxidation number.
[4]

The reaction in (ii) is not redox. There is no


electron transfer/change in oxidation number.

3 a The size of an atom is determined by the attraction


of the nucleus for electrons and the shielding of
outer electrons from the nucleus by inner shells of
electrons.[3]

b i

This is because the sodium ion, Na+, has one


less shell of electrons compared to the sodium
atom. Consequently, there is a decrease in
shielding and an increase in the nuclear charge
experienced by each electron.
[2]

ii This is because with increasing proton number,


each successive positive ion contains an
additional shell of electrons. The additional
screening or shielding effect outweighs the
effect of increased nuclear charge.
[2]
c The magnesium ion has 12 protons and 10 electrons;
the sodium ion has 11 protons and 10 electrons. The
nuclear charge of the magnesium ion (+12) is greater
than the sodium ion (+11). Consequently, all the
electrons in the magnesium ion will experience a
greater force and be located nearer to the nucleus.[2]

d i

N < N [1]
3

ii Fe3+ < Fe2+ < Fe

4 The ions formed across period 3 would be Na+, Mg2+,


Al3+ and P3, S2 and Cl.

There is a decrease in ionic radii from Na+ to Al3+: all


the ions have the electron arrangement of 2, 8 (i.e.
they are isoelectronic); however, there is a progressive
increase in the nuclear charge due to the additional
protons: the sodium ion has 11 protons, the magnesium
ion has 12 protons and the aluminium ion has 13
protons. All of the electrons experience a higher
effective nuclear charge and the electrons in the two
shells are pulled progressively towards the nucleus.

There is a decrease in ionic radii from P3, S2 to Cl: all


the ions have the electron arrangement of 2, 8, 8 (i.e.
they are isoelectronic); however, there is a progressive
increase in the nuclear charge due to the additional
protons: the phosphide ion has 15 protons, the sulfide
ion has 16 protons and the chloride ion has 17 protons.
(All of the electrons experience a higher effective
nuclear charge and the electrons in the three shells are
pulled progressively towards the nucleus.)
[6]

5 a Ionization energy increases.


Nuclear charge increases/electron is closer (on


average) to the nucleus/atomic radius decreases. [2]
b Aluminium is lower than expected; sulfur is lower
than expected.

In aluminium the electron removed is in a p subshell/at a higher energy than in magnesium.

The s electron removed is in an orbital that


contains a second electron that repels it/change to a
half-filled p sub-shell.
[4]

6 Across period 3 of the periodic table, the oxides of the


elements change from basic to amphoteric to acidic
innature due to the increasingly electronegativity of
the elements,which gradually changes the bonding
from ionic to covalent.

Sodium and magnesium oxide react to form hydroxide


ions:

Na2O + H2O 2NaOH; MgO + H2O Mg(OH)2


Aluminium oxide is amphoteric and reacts with both


acids and bases:

Al2O3 + 6H+ 2Al3+ + 3H2O;


Al2O3 + 2OH + 3H2O 2Al(OH)4

Silicon dioxide is an acidic oxide and reacts with hot,


concentrated alkali:

SiO2 + 2OH SiO32 + H2O


The highest oxides of the remaining non-metallic


elements react with water to form strongly acidic
solutions:

P4O10 + 6H2O 4H3PO4; SO3 + H2O H2SO4;


Cl2O7 + H2O 2HClO4

[3]

[1]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

4 Chemical bonding and


structure

b The CCl bond is more polar than the NCl


bond. Nitrogen is more electronegative than
carbon. NCl3 is polar; CCl4 is polar. The NCl3
molecule is not symmetrical and dipole moments
do not cancel; CCl4 is symmetrical and the four
dipole moments cancel.
[5]

Paper 1
1 A

15 A

2 A

16 B

3 B

17 D

4 B

18 C

5 A

19 D

6 C

20 A

7 D

21 A

8 C

22 A

9 B

23 B

10 C

24 A

11 D

25 A

12 D

26 A

13 B

27 A

14 A

28 A

3 Ethanol and water are miscible in each other due to the


formation of hydrogen bonding. The ethane molecule
is non-polar and is not able to form hydrogen bonds
with water molecules.
[2]

4 a Potassium metal has a lattice of unipositive ions


(cations) in fixed positions with a sea of delocalized
or mobile valence electrons that are free to move
through the lattice. The metal is held together by
attraction between the nuclei of the positive ions
and the delocalized electrons.
[4]
b Lewis structure for fluorine:

Paper 2
1 Sodium, magnesium and aluminium are metallic
and hence are good electrical conductors due to the
presence of delocalized valence electrons. From sodium,
magnesium to aluminium, the atomic and ionic size
decrease and the number of valence electrons available
for delocalization increases from one to three. Thus,
the metallic bonding strength increases and hence
the melting point increases since more heat energy is
required to break the metallic bonding. In addition,
with more valence electrons for delocalization, the
electrical conductivity also increases.
[3]

The bonding within a fluorine molecule is a single


covalent bond. This consists of a shared pair of
valence electrons.
[1]

The bonding between molecules arises from


London (dispersion) forces. These involve the
attraction between dipoles temporarily set up by
electron polarization.
[1]
c The potassium atom has the configuration
2, 8, 8, 1. 

[1]

The fluorine atom has the configuration 2, 7.

Potassiums outer electron is transferred to the outer


shell of the fluorine atom.
[1]

Oppositely charged ions are formed (with complete


octets of electrons) which attract each other due to
electrostatic forces of attraction.
[1]

[1]

d The ions are not free to move in the solid state.


However, they can move in the molten state under
the influence of a voltage.
[1]
5 a Boron trifluoride is a simple molecular substance
and aluminium fluoride is ionic.
[6]
+
+

++

++

+
+

+
+

+
+

3+

AI

++

[2]

++

The triple bond in the nitrogen molecule is


stronger and hence harder to break.

+
+

Silicon has a giant covalent structure with strong


siliconsilicon single bonds. A large amount of heat
energy is required to break all these bonds and hence it
has a high melting point. Phosphorus (P4), sulfur (S8),
chlorine (Cl2) and argon (Ar) are simple molecular
covalent substances and hence are held together in
the solid state by London (dispersion) forces. A small
amount of thermal energy is required to break these
intermolecular forces and hence their melting points
are low. The strength or extent of London (dispersion)
intermolecular forces increases with molecular size
(number of electrons). Thus, sulfur has the highest
melting point followed by phosphorus, chlorine and
then argon.
[3]

2 a Electron dot structures for N2 and F2:[2]


Ethane molecules can only form weaker London


(dispersion) forces with water molecules. Cholesterol
has a polar alcohol group; however, it behaves as a nonpolar molecule due to the relatively large size of the
hydrocarbon group.
[2]

[1]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015


b i

d Significant heat loss to the surroundings.


Insulate the reaction vessel and use a lid. Draw a
temperature versus time graph and extrapolate to
calculate the rise in temperature.
[2]

A coordinate covalent bond. Both electrons


are supplied by the nitrogen atom of ammonia
which has a lone pair of electrons.
[2]
+
+

ii

++

++

B N H
+

+
+

[2]

e The temperature change would be the same,


namely, 3.5C. This occurs because the amount of
lithium hydroxide reacted would be the same. The
excess hydrochloric acid would not react; lithium
hydroxide is the limiting reagent.
[2]

5 Energetics/thermochemistry

3 a The enthalpy change that occurs when one mole


of a pure compound is formed under standard
thermodynamic conditions from its elements in
their standard states.
[2]

Paper 1
1 C

10 A

2 D

11 A

3 D

12 D

4 D

13 A

5 A

14 C

6 B

15 A

7 B

16 D

8 A

17 C

b The enthalpy change that occurs when one mole of


a pure compound undergoes complete combustion
in the presence of excess oxygen under standard
conditions.[2]
c Hesss law states that the total enthalpy change for
a reaction is independent of the route taken.
It depends only on the initial and final states.
[1]

9 D

C3H8 (g)

+ 5O2(g)

1 a i

The energy needed to break one mole of a


particular covalent bond in a molecule in the
gaseous state and form gaseous atoms.

The value is averaged using those from similar


compounds.[3]

Sum of bonds broken = 412 + 158 = 570kJ

H = 476kJmol1[3]
CH4 + F2
enthalpy

[2]

CH3F + HF

iii About the same since the same number and


type of bonds are being broken and formed. [2]
2 a It is exothermic because heat is released to the
surroundings and the temperature rises.

According to Hesss law, H1 = H2 H3

H1 = Hf [C3H8(g)]
H2 = 3 Hc [Cgraphite] + 4 Hc [H2(g)]
H2 = 3 (393kJmol1) + 4 (286kJmol1)
= 2323kJmol1
H3 = Hc [C3H8(g)] = 2220kJmol1

Sum of bonds formed = 484 + 562 = 1046kJ

ii

H3

3CO 2(g) + 4H2O(l)

ii It is an element and is the only species with a


FF bond.
[1]
b i

+ 5O2(g)
H2

Paper 2

H1

d 3C(s) + 4H2(g)

Hence,
Hf [C3H8(g)] = (2323kJmol1) (2220kJmol1)
=103
kJ
mol1[4]

6 Chemical kinetics
Paper 1

[1]

1 A

5 D

b To make any heat loss as small as possible, so that


all the heat will be given out very rapidly.
[1]

2 B

6 A

3 C

7 C

c Heat released = mass specific heat capacity

temperature increase

Amount of LiOH or HCl used =


0.500dm3 0.050moldm3 = 0.025mol

Heat released = 100g 4.18Jg1C1 3.5C

=1463
J = 1.463
kJ

H = (1.463kJ 0.025mol) = 58.5kJmol1[4]

4 C

Paper 2
1 a i

Carbon dioxide, CO2[1]

ii CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g)


+H2O(l)[2]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015


b 800cm3; 8 minutes

c i

The collision frequency between carbonate


and hydrogen ions is greatest at the start, but
decreases with time. The concentrations of
the two reactants is highest at the start of
the reaction. However, as the chemicals react
the number of reacting ions decreases the
concentrations and hence the collision rate
decreases.[2]

ii The mass of calcium carbonate may be less


in Y and hence greater in X.

[1]

The concentration of hydrochloric acid may


be less in Y and hence higher in X.
[1]

2 a i

30cm3[1]

ii

19cm3[1]

iii 9cm3[1]
b As the reaction proceeds the surface area of the
magnesium (the limiting reagent) decreases. The
magnesium is being used up, and hence the rate
decreases. The acid remains in excess and its
concentration remains relatively constant.
[2]

7 Equilibrium
Paper 1
1 A

8 A

2 D

9 B

3 A

10 A

4 D

11 D

5 C

12 C

6 D

13 B

7 B

c The reaction has stopped; all of the magnesium has


been consumed.
[1]

Paper 2

d Plot an accurate graph of the results: labelling the


axes, plotting points carefully, and drawing a curve
of best fit.
[3]

Rate of forward process/reaction = rate of


backwards/reverse process/reaction

Rate of vaporization/evaporation = rate of


condensation;

Concentrations of reactants and products remain


constant;

There is no change in macroscopic properties in a


closed system;

Do not accept concentration of reactants and products


are equal.

Accept constant colour of Br2 vapour/liquid.

Parts i and ii; draw tangents to your curve and


estimate the slopes at the two points. 
e i

[1]

ii Initial rate decreased

[1]

iii Initial rate increased

[1]

f i

Final volume of gas increased

g i

1 a Any one of the following statements: 

[4]

Initial rate increased

ii Final volume of gas unchanged


b The rate of a reaction increases with temperature as


the particles are moving faster (have greater kinetic
energy) and therefore collide more frequently
[1]
The colliding particles are more likely to have
combined kinetic energy greater than the activation
energy of the reaction and so more collisions
produce a reaction.
[1]
The second of these factors is the more significant/
important of the two.
[1]

[2]

[1]
[1]

Use to measure one of the following: gas


pressure, motion or change in mass using a
balance connected to computer.

[2]

Could not use: light sensor.

[1]

b i Kc =

Increasing the concentration of H2O2 will


increase the rate of reaction as the frequency
of collisions will increase as there are more
particles present.
[2]

ii This will have no effect; the concentration


of NaI does not depend on the size of the
crystals used to make the solution, just the
mass used.
[2]

[SO 2 ]2 [O 2 ]

[1]

ii Two or three correct [1]; four or five correct [2];


all correct [3]

ii Give a brief description of one use: pressure


sensor fitted to sealed flask detecting increase
in pressure with time; motion sensor detecting
movement of gas syringe barrel with time;
balance detecting loss in mass of flask and
contents with time.
[3]
3 a i

[SO 3 ]2

[1]

Position of
equilibrium

Value of Kc

Decrease in temperature

Shifts to right/
products

Increases

Increase in pressure

Shifts to right/
products

No effect

Addition of catalyst

No effect

No effect

c i

Minimum/least/smallest energy needed (by


reactants/colliding particles) to react/start/
initiate a reaction.

[1]

Allow energy difference between reactants and


transition state.

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015


ii

Probability of molecules

T1

Equilibrium established when rate of forward


reaction = rate of reverse reaction.
[7]

b Reaction is endothermic
Kc increases with (increasing) temperature
the forward reaction favoured/heat is used up.

T2

4 a 200C [1] and 600 atm [1].



(Kinetic) energy

[1]
[1]
[1]
[2]

(Allow the highest pressure and the lowest


temperature.)
b i

Yield increases/equilibrium moves to the right/


more ammonia.
[1]

The x-axis label: (kinetic) energy; the y-axis


label: probability/fraction of molecules/particles/
probability density.

Allow number of molecules/particles for y-axis.

Correct shape of a typical MaxwellBoltzmann


energy distribution curve;

ii Yield decreases/equilibrium moves to the left/


less ammonia; exothermic reaction.
[2]

Do not award mark if curve is symmetric, does not


start at zero or if it crosses x-axis.

Two curves represented with second curve for


T2>T1 to right of first curve, peak maximum lower
than first curve and after the curves cross going to
the right, T2 curve needs to be above T1 curve as
illustrated.[2]
[HI]2
[1]
2 a Kc =
[H 2 ][I2 ]

Lower temperature: greater yield, but lowers rate. [2]

(Do not award a mark for simply saying compromise.)


[NH 3 ]2
[1]
d Kc =
[N2 ][H 2 ]3

e i

[1]

d As the reaction is endothermic, increasing the


temperature will shift the equilibrium position to
the right (more product formed).
[1]
3 a Two curves one labelled forward starting up high
up y-axis and one labelled reverse starting from
zero. The curves merge and become horizontal.

Rate

forward

reverse

Time

Forward reaction highest concentration,


thus rate high to begin with. As the reaction
proceeds, the concentrations decrease, as does
the rate.

ii Reverse reaction zero rate initially at t = 0


(since no products present). The rate increases
as concentration of products increases.

Artificial fertilizers/increasing crop yields;


production of high explosives for mining
[1max].[1]

ii Fe/iron (allow magnetite/iron oxide).

b Concentration of product / HI greater


(than [H2] and [I2])[1]

[1]

c High pressure expensive/greater cost of operating at


high pressure/reinforced pipes, etc. needed.

c It will have no effect. 

4 (gas) molecules 2/decrease in volume/


fewermolecules on right-hand side.

[1]

The claim is not valid since catalysts do not


alter the yield/position of equilibrium they only
increase the rate of reaction.
[1]

8 Acids and bases


Paper 1
1 D

14 B

2 C

15 D

3 A

16 B

4 C

17 D

5 D

18 D

6 A

19 A

7 A

20 A

8 D

21 C

9 B

22 A

10 D

23 C

11 B

24 B

12 A

25 B

13 D

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

9 Redox processes

Paper 2
1 a i

Acid X

[1]

ii A factor of 10

[1]

iii Y, Z and X

[1]

Conductivity increases with ion concentration.


As the pH value decreases the concentration of
hydrogen ions increases.
[1]

2 a A strong acid is fully ionized or dissociated in


solution.[1]
HCl(aq) H+(aq) + Cl(aq)[1]

A weak acid is partly ionized or dissociated in


solution.[1]

H2CO3(aq) 2H+(aq) + CO 32 (aq)[1]


or
H2CO3(aq) H+(aq) + HCO3 (aq)
b Universal indicator: hydrochloric acid red;
carbonic acid yellow/orange.

Paper 1
1 A

10 D

2 D

11 D

3 D

12 C

4 A

13 B

5 A

14 C

6 B

15 B

7 D

16 D

8 D

17 A

9 B

Paper 2
1 a i

[1]

ii The loss or removal of electrons from a


chemical species.

Electrical conductivity: hydrochloric acid high;


carbonic acid low
or

Reaction with metal/metal carbonate: hydrochloric
acid vigorous; carbonic acid slow.
[1]

Acid: HCl; conjugate base: Cl[1]

Copper(ii) ions gain electrons during their


reaction with iron atoms:

[1]

Cu2+(aq) + 2e Cu(s)

3 a Both solutions have an excess of hydroxide ions,


which can accept protons to form water molecules.[1]

OH is a base/conjugate base and C 2 H 5 NH 3+ is a


conjugate acid/acid
[1]

d C2H5NH2(aq) + HCl(aq) C 2 H 5 NH (aq)


+ Cl(aq)[1]
[1]
[1]

source of current [1]

b HSO (aq) and H2O(l)[1]


c Nitric(v) acid, HNO3[1]

[1]

It is too low in the reactivity series and hence


isless reactive than magnesium.
[1]

[4]

electrodes [1]
correct polarity with reference to battery [1]
molten salt [1]

d Leaching of minerals into freshwater lakes; killing


of young fish
[2]

H2SO3(aq) Y 2H+(aq) + SO32(aq)

Every metal present can reduce gold ions to


gold atoms.
[1]

vi Does not react.

+
3

e S(s) + O2(g) SO2(g);


SO2(g) + H2O(l) H2SO3(aq)[3]

It reduces Fe2+; Fe reduces Cu2+; Cu


reduces Au+.[1]

v Gold ions, Ag+[1]

c C2H5NH2(l) + H2O(l) C 2 H 5 NH 3+ (aq)


+ OH(aq)[1]

4 a Proton (H+) donor

[1]

iv Magnesium (Mg) is the strongest reducing


agent.[1]

b The pH of potassium hydroxide solution would


be higher. This is because it is a stronger base
than ethylamine. It hence undergoes greater
dissociation.[3]

e It is a strong acid and hence corrosive.

Iron atoms lose electrons during their reaction


with copper(II) ions:

iii Reduction involves a decrease in oxidation


number.[1]

d i Base: HCO3 ; conjugate acid: H2CO3[1]


ii Brnsted-Lowry

[1]

Fe(s) Fe2+(aq) + 2e[1]

c 10000:1 or 104:1 or 0.1:0.00001 or 101:105[2]


Magnesium (Mg), iron (Fe), copper (Cu), and


gold (Au).
[1]

c At the cathode (negative electrode):


electrons are given to the cations (positive ions) [1]

electrons are removed from the anions


(negativeions).[1]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

At the anode (positive electrode):

copper atoms formed (at the cathode)

[1]

chlorine molecules formed (at the anode).

[1]

b Molar mass of empirical formula = 71.

2 a At the negative electrode (cathode):

Molecular formula of hydrocarbon = C10H22[1]


ii 2C10H22 + 21O2 20CO + 22H2O[2]

Electrons flow through the external circuit or wires


and the ions move through the electrolyte to the
electrodes where they gain or lose electrons.
[4]
b 0.2mol since the K to F2 molar ratio is 2:1.
c i

[2]

ii

ii C5H10[1]
2 a i

ii Amount of Fe2+ = 5 2.32 104

= 1.16 103mol

B or C: CH3COOCH3 methyl ethanoate.

C or B: HCOOCH2CH3 ethyl methanoate.

[1]

A ionizes/dissociates to give H+ ions.

[1]

ii C2H5COOH + NaOH C2H5COONa


+ H2O[1]
iii No C=C bond.
[1]

100

d A has the highest boiling point as the acid molecules


have the capability of hydrogen bonding together; B
and C have similar boiling points as they are both
esters, their boiling points are lower than that of A
as they cannot take part in intermolecular hydrogen
bonding.[2]

Paper 1
7 D

2 B

8 C

3 B

9 D

4 A

10 B

5 C

11 A

6 B

12 C

e i Ester

ii Carboxylic acid/alkanoic acid [1]; alcohol/


alkanol [1]; water [1].

[3]

f Any feasible formula containing C=C (e.g.


CH3CHC(OH)2 or HOCH=C(OH)CH3).[1]
Addition
[1]

Therefore empirical formula is C5H11

[1]

Flavourings/plasticizers/solvents/perfumes [1]

Paper 2
1 a Molar ratio = 1:2.2.

[6]

c i A forms hydrogen bonds with water.

10 Organic chemistry
1 D

Molecular formula = 2 empirical formula

=C2H4O2[2]

b A: CH3CH2COOH / CH3CH2CO2H propanoic acid.

% of Fe2+ in tablet = 6.48 10


1.43
= 4.53%

[2]

CH3CH2CH2CH3, butane / CH3CH(CH3)CH3,


2-methylpropane.[4]

iii Mass of Fe = 55.85 1.16 10


= 6.48 102g

Molecular formula = 2 empirical formula


=C4H8O2[2]

3 a Full or condensed structures:

iii MnO4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O


11.6
b i Amount of MnO4 =
0.0200
1000

= 2.32 104mol

Empirical formula is C2H4O[3]

b i Empirical formula is CH2O


ii Molar mass of empirical formula = 30.

[2]

MnO4 + 8H+ + 5e Mn2+ + 4H2O

2+

% Oxygen = 36.4

ii Molar mass of empirical formula = 44.

3 a i Fe2+(aq) Fe3+(aq) + e

Could also have an equation where C is produced.

d i C4H10[1]

Sodium atoms lose electrons and undergo


reduction. Aluminium ions (in aluminium
chloride) gain electrons and undergo
oxidation.[2]

ii Reactants: sodium metal: 0; aluminium in


aluminium chloride: 3
Products: aluminium metal: 0; sodium in
sodium chloride: +1

Molecular mass = 142; therefore molecular formula


= 2 empirical formula.

At the positive electrode (anode):

2F F2 + 2e

c i 2C10H22 + 31O2 20CO2 + 22H2O[2]

K+ + e K

[1]

[1]
[1]

Mixture is decolorized/colour change is from yellow/


orange to colourless.
[1]

4 a i

Same general formula/differ by CH2/similar


chemical properties/gradual change in physical
properties.[3]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 10


ii

CH3

CH2

CH2

CH2

OH

[4]

6 a i

CH3
CH3

II

CH3


OH

H
CH3

III

OH

C2H5

Empirical formula is C19H20N2O2[3]


ii Mr of empirical formula = actual Mr
Molecular formula is C19H20N2O2[1]
iii (0.5) (40 20 2) = 9
[1]
b A is carboxamide (amide); B is phenyl; C is
carboxyl (carboxy); D is hydroxyl.
[2]

b i

CH3

IV

CH3

CH2

OH

11 Measurement and data


processing

Esterification / condensation CH3COOH +


C2H5OH CH3COOC2H5 + H2O
O
CH3

C
O

Paper 1

C2H5

1 B

8 B

[4]

2 D

9 D

ii Catalyst; lowers activation energy (by providing


an alternate pathway) 
[2]

3 C

10 C

iii Flavouring agents / in plasticizers / in solvents /


in perfumes 
[1]

4 B

11 C

5 C

12 B

6 A

13 C

c i

Ethyl ethanoate

II reacts with bromine / contains C=C / II is an


alkene / has unsaturated R group.
I contains only saturated R groups.

[2]

ii Addition polymerization
CH

7 B

Paper 2
1 a i

CH2

CHO

[1]

ii Propan-1-ol

[1]

iii 2-Methylbutan-2-ol

[1]

iv Ethane-1,2-diol

[1]

b i Secondary

[1]

ii Primary

[1]

iii Tertiary

[1]

iv Primary

[1]

c i

Propanone, CH3COCH3[2]

ii Propanoic acid, CH3COOH[2]


iii No oxidation

[1]

iv Ethane-1,2-dioic acid, HOOCCH2CH2COOH[2]

The actual volume of sodium hydroxide will be


lowered, and the calculated concentration of
hydrochloric acid will be higher.
[2]

ii If there was water in the burette, the sodium


hydroxide would be diluted, lowering the
amount of sodium hydroxide and the
concentration of hydrochloric acid.
[2]

[2]

5 a i Propan-2-ol

73.99
= 6.161
12.01
6.55
Number of moles hydrogen =
= 6.49
1.01
9.09
Number of moles nitrogen =
= 0.649
14.01
10.37
Number of moles oxygen =
= 0.648
16.00
C:H:N:O molar ratio is 9.5:10:1:1

Number of moles of carbon =

iii This will make the concentration of the


hydrochloric acid appear greater than it is.

[1]

iv The end point will not be accurate, causing


random errors.
[1]

b i

Systematic error.

[1]

ii Measure the pH of a buffer solution of known


pH value.
[1]
2 a Mass of copper (dependent), time (independent)
and current (controlled variable).
[3]
b Directly proportional.
[1]
mass of copper(g) 1.24 g
1
=
c Rate =
= 0.08gmin [2]
time(min)
15min
d Interpolation, area under the graph and
extrapolation.[2]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 11


1
100
3 a Percentage uncertainty in length =
298

=0.336%[1]
1
b Percentage uncertainty in width =
100
210
=0.476%
c Area = 298mm 210mm = 62580mm2[1]
1
1
+

Percentage uncertainty in area =


298 210
62580 = 508mm2

Area = 62580mm2 508mm2[2]
4 a The bond angle (HSH) changes as bending
occurs.[1]

The lengths of the SH bonds change as stretching
occurs.[1]

The dipole moment of the molecule changes.
[1]

b i

Absorptions in NMR are due to transitions


between different spin states in the nucleus
(when an external magnetic field is applied). [1]
[1]

[4]

[3]

12 Atomic structure
Paper 1
1 A
2 A
3 C
4 B
5 A
6 D
7 B
8 C

9 A
10 A
11 B
12 C
13 C
14 D
15 D
16 B

IR absorptions are due to bond vibrations.

The nuclear transitions are at a much lower


energy than bond vibrations.
[1]

Paper 2

There is an inversely proportional relationship


between frequency and energy.
[1]

1 a The first ionization energy is the minimum


energy required to remove one mole of electrons
from one mole of gaseous atoms to form one
mole of unipositive gaseous ions (under standard
thermodynamic conditions).
[2]

energy =

Plancks constant velocity


;
wavelenght

energy
wavenumber = Plancks constant velocity [2]
d Atomic masses increase from chlorine to iodine. [1]
Heavier atoms vibrate more slowly and hence the
stretching frequency decreases.
[1]

5 a P: +CH3, Q: +C2H5 and R: +C3H7[3]


b

(ratio of areas or integration traces in)


1-iodobutane: 3:2:2:2
(ratio of areas or integration traces in)
2-iodobutane: 3:1:2:3
b 1-fluoro-2-methylpropane has three peaks:
(ratio of areas or integration traces in)
1-iodobutane: 2:1:6

ii The bond in both molecules vibrates and


stretches; only the stretching in the hydrogen
bromide, HBr, causes a change in dipole
moment.[2]
1
c wavenumber =
;
wavelength (cm)

Information

Analytical technique

Relative atomic mass of an


element

Mass spectrometry

Functional groups and


strength of bonds present in
an organic molecule

Infrared spectroscopy

Potassium ions in a sample of


blood serum

Atomic absorption
spectroscopy and
inductively-coupled
plasma spectroscopy

Detailed structure of an
organic molecule (without
degrading the sample)

Nuclear magnetic
resonance

[3]

6 a Both 1-fluorobutane and 2-fluorobutane have four


peaks:

b In a group 2 element (C) the electron (for the first


ionization energy) is removed from a spin pair in an
s sub-shell. For D, a Group 13 element, the electron
(for the first ionization energy) is removed from a
3p sub-shell further away from the nucleus. The 3p
sub-shell also experiences more shielding. Hence
there is a decrease in first ionization energy when
moving from C to D. The increase in nuclear charge
accounts for the increase from E (np2 to F np3). In
addition C cannot be in Group 15 (the other group
after which there is a slight decrease) because there
is a steady rise for the next 3 elements (D to E to F)
indicating the filling of a p sub-shell.
[4]
c As you move down group 2 the first ionization
energies decrease. As you descend the group the
nuclear charge increases due to the presence
of additional protons, but the shielding effect
progressively increases due to the presence of an
extra electron shell as you move from one period
to the next. The effect of the extra protons is
compensated for by the effect of the extra electrons.
The only factor left is the additional distance
between the outer electron and the nucleus. That
lowers the first ionization energy.
[3]
d C is in period 3 since in period 2 the Group 2
element would have the higher ionization energy
while in period 4 the Group 2 element would have
a lower ionization energy. This can be accounted for
by the progressively increasing average distance the

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 12


valence electron is from the nucleus. C cannot be in
the first period (He) as p-orbitals are being filled, it
cannot be in the fourth period (Ca) as (x + 8) would
not bring you back to Group 2 again.
[3]
e There is a slight decrease from F to G due to the
presence of a spin pair in the np sub-shell for G.
The resulting electronelectron repulsion is greater
than the effect of the increase in nuclear charge
and reduces the ionization energy of G+.[2]

Paper 2
1 a Ester functional group.
b Coordinate covalent bond.

The p sub-level is of higher energy/further from


nucleus (than the s sub-level)/experiences greater
shielding from nucleus.
[2]
c The third electron is more difficult to remove
because it is taken from a positively charged ion and
from a (main) energy level closer to nucleus / from
second energy level/n = 2 while the first electron
comes from the third energy level/n = 3.
[1]
d 1s2 2s2 2p6 3s2 3p6 3d7 4s2; 4s

3 a 4p

[2]
[1]

b Ge+(g) Ge2+(g) + e[1]


c The germanium atom contains four valence
electrons: 4s2 and 4p2. There is a steady increase
in ionization energy. Upon reaching the fifth
ionization energy an electron must be removed from
a completely filled inner 3d sub-shell. Once filled
these act as core electrons and this is reflected in
the large increase in ionization energy.
[2]

13 The periodic table the


transition metals
Paper 1
1 A

9 A

2 A

10 A

3 B

11 D

4 B

12 D

5 A

13 D

6 A

14 A

7 A

15 C

8 B

16 D

[2]
y

x
s orbital

px orbital

ii 16

Mg(g) Mg+(g) + e[3]

[1]

c i


2 a The energy needed to remove one mole of valence


electrons from a mole of (neutral) atoms; in the
gaseous state:
b The electron removed (from aluminium) is in a p
sublevel/sub-shell while that from magnesium is in
an s sub-level/sub-shell.

[1]

[1]

d 1s 2s 2p 3s 3p 3d 4s 4p 4d [1]
2

3s

3p

10

4s

3d

[1]

2 a A pale blue precipitate of hydrated copper(ii)


hydroxide, Cu(OH)2. The precipitate reacts with
excess ammonia to form a solution containing a
deep blue complex ion:
Cu2+ + 2OH Cu(OH)2
2+
Cu(OH)2 + 4NH3 [Cu(NH3 )4 ] + 2OH[4]

b i 4H+ + 3 MnO4 2 2 MnO4 + MnO2 + 2H2O[2]


ii +6, +7 and +4
[3]
iii Catalysis
[1]
2+
10
c The zinc ion, Zn has a 3d electron configuration
(fully occupied 3d-orbitals). Hence it is not possible
to have dd transitions and it is thus colourless. [2]
3 a +3 and +2
[2]
b Six cyanide ligands are coordinated octahedrally to
a central iron(ii) ion.
[2]
c A transition metal is a metal that forms compounds in
which the metal has a partially filled 3d sub-shell. [1]
d Hemoglobin is an iron-containing protein found
inside red blood cells. The iron forms a complex
with oxygen, known as oxyhemoglobin, when
the oxygen concentration is high. At low oxygen
concentrations the oxygen is released and
hemoglobin is re-formed.
[2]
hc
4 E = ; so the larger the wavelength, the smaller the

energy, so Z>Y>X.[3]
hc
; E = (6.63 1034Js 3.00 108m s1)

1 109m 1/1000 6.02 1023 = 163kJmol1[4]

5 E =

6 a +3
[1]
b 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 4d6[1]
c 4
[1]
d Octahedral

[5]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 13

14 Chemical bonding and


structure

3 a Each correct structure (with non-bonding electron


pairs where relevant)
C2H2 linear/straight

Paper 1

Angle 180
H

1 A

11 C

2 B

12 D

C2Cl4 (trigonal) planar

3 C

13 C

4 D

14 D

5 A

15 B

6 C

16 C

7 C

17 C

8 D

18 A

SF4 K-shaped/based on trigonal bipyramid/see-saw

9 B

19 A

Angle 90

10 B

20 B

Angle 120

+
+

+
+
+

+
+

+
+
+
+

[1]
4

2 a

++
+

++

c The right-hand one.

++
+
+ + ++
+
+
+
+
+ ++
+
+
+
++

+
+

[2]

Cl

++

++

Cl

++

++

[1]

Cl

++

++

Cl

++

++

Paper 2
b +2 and 0

Angle 120

1 a The left-hand one.

+ ++
+ ++

S F

[10]

b sp (C2H2)
sp2 (C2Cl4)[2]

2
[2]
2p

Energy

2p

c
[2]

2s

2s
OB

b 2s(OA) and 2s(OB) combine to form 1 and 2*.

2pz(OA) and 2pz(OB) combine to form 3 and 4*.[2]


c 2px(OA) and 2px(OB) combine to form one pair
of 1 and 2*.
2py(OA) and 2py(OB) combine to form one pair
of 1 and 2*.

C
O

[2]

4 a Sigma bonds involve an overlap of orbitals end-on/


along the molecular axis (it has axial symmetry around
axis joining the two nuclei) overlap of s orbitals.

1
O2

OA

CH3

CH3

Pi bonds result from overlapping of parallel p


orbitals/sideways overlap.
Double bond: a sigma bond and a pi bond.
Triple bond: a sigma bond plus two pi bonds.
p orbitals: head-on overlap: sigma bond formation

sigma molecular orbital

s orbitals overlap: sigma bond formation

sigma molecular orbital

[4]

[2]

d (1) (2*) (3) (1) (2*) .[1]


2

e Paramagnetic. Paramagnetic refers to the magnetic


state of an atom, ion or molecule with one or more
unpaired electrons. The unpaired electrons are
attracted by a magnetic field due to the electrons
magnetic dipole moments.
[2]
f Two

p orbitals: sideways overlap: pi bond formation

internuclear axis

[1]

g If four electrons are added to O2, the bond order


will reduced to zero. This will generate two oxide
anions: O2 + 4e 2O2.[2]

pi molecular orbital

atomic orbitals

molecular orbitals

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 14


b Delocalization: when pi electron pairs are not
confined to two adjacent bonding atoms but extend
over three or more atoms.[2]
5 a Lewis electron dot structures for PBr3 and PBr5:

++

+
+

+
++

+ ++
+
+

Br

Br

Br
Br

Br

Related to standard conditions or 298K


(or 25C) and one atmosphere pressure.

Br

Ion

[PBr4]+

Number of electrons in
valency shell of central
phosphorus atom

(5 + 4 1) = 8

Number of electron pairs


contributing to basic
molecular shape

Molecular shape

Tetrahedral

[4]

iii Hf (Cu) = 0 (by definition an element is in


its standard state)
[1]
b i Hf reaction = Hf products Hf reactants
[1]
Hf reaction =([4 (242) + (1084)] [2278])
[1]
= +226
kJ
mol1

[1]

(adjusting for ionic


charge)

15 Energetics/thermochemistry
1 C

9 B

2 D

10 D

3 D

11 C

4 B

12 A

5 B

13 A

6 A

14 C

7 B

15 A

8 D

16 C

[1]

An endothermic process or reaction needs heat


energy.[1]

ii S reaction = S reactants S products


= (4 (189) + (150) ) (305)  [1]
S reaction = 601JK1 mol1 or
0.601kJK1mol1[2]

d The hybridizations of the phosphorus in


phosphorus(iii) bromide and the oxygen in water
are sp3 and sp3, respectively.
[2]

Paper 1

[1]

ii was not included because S has absolute


values; S values can be experimentally
measured.[1]

Br

The bond angle in PBr3 is approximately 107 since


a lone pair of electrons (due to its more diffuse
nature) produces more repulsion than a bonding
pair, hence the bond angle is reduced below the
tetrahedral bond angle of 109 28.
[4]
c

It is related to the disorder or randomness of


particles.[1]

b The bond angles present in PBr5 are 90 and 180,


respectively.

+
+

Br

S represents the standard or absolute


entropy.[1]

+
+
+

++

Br

Molecular shapes for PBr3 and PBr5:

++

+
+

+
+

It is the heat change (absorbed or released


under constant pressure) when a mole of a
compound is formed from its elements in
their standard states.
[1]

+
+
+

[1]

Br

+++

++

++
+
+
+
+
+ ++
+
+
+
++
+

++

Br

1 a i Hf is the standard enthalpy change of


formation of a substance.

+
+

+
+

Br

+
+

Br P Br

Paper 2

(+) sign/value, thus products more disordered


than reactants.
[1]

iii Gibbs free energy (G).[1]



c i

Units: kJmol1[1]
At 25C, G = H TS

G = (+226)kJmol1 (25+273)K
601

kJmol1K1[2]
1000
G = +46.9kJmol1[1]

As the value of the Gibbs free energy change,


G, is positive at 25C, the forward reaction
is not spontaneous. However, this implies
that the backward reaction is spontaneous.
Hence, at 25C, CuSO4.5H2O(s) is the
thermodynamically more stable compound. [2]

ii When both compounds have equal


thermodynamic stabilities, the Gibbs free
energy change will be zero, ie, G= 0.
G= H TS

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 15

601 1 1
0 = (+226kJmol1) T
kJ K mol [1]
1000
1
226kJmol
T=
= 376K (103C)
[1]
0.601kJK 1mol 1
Hence, CuSO4.H2O(s) is more
thermodynamically stable above 103C.
[1]

2 a The lattice enthalpy is the energy needed to break


down one mole of ionic solid into gaseous ions
(separated to a infinite distance) under standard
thermodynamic conditions (1 atm and 25C). [2]
b The greater the charge on the ions, the higher
the value of the lattice enthalpy. Larger charges
produce greater electrostatic forces of attraction
between oppositely charged ions.
[1]

S = [214 + 70] [112] = +172kJmol1


G = 267 (298 (0.172) = +216kJmol1[6]
b Non-spontaneous as G is positive.

16 Chemical kinetics
Paper 1
1 C

6 D

2 C

7 D

3 D

8 D

c Born-Haber cycle for rubidium oxide, Rb2O:[2]

4 C

9 D

2nd EA(O)
2Rb

+(g)

2e

2 IE(Rb)

5 C

Paper 2

+ O(g)

1st EA(O)
2Rb+(g) + e + O(g)

1 a The factor A is indicative of frequency of collisions


and the probability that collisions have the proper
orientation to react.
[1]
b k = exp[(87.0 1000 / 8.31 298) + ln(2.10 1011)]
= 1.2 104mol1dm3s1

2Rb(g) + O(g)
Hat(O)
2Rb(g) +

1
2

LE(Rb2O)

O2(g)

2Rb(s) + 12 O2(g)

Change in concentration of reactant/product


with time or rate of change of concentration.[1]

ii Concentration; particle size / surface area; light;


pressure.[2]

Hf(Rb2O)

These units are chosen as this is an SN2 reaction


which implies it is second order.
[2]

2 a i

2 Hat(Rb)

The factor TS predominates and G becomes


negative; TS must be greater than H for G to
be negative.
[4]

The smaller the ionic radius, the higher the value


of the lattice enthalpy. Smaller ions can approach
each other more closely and hence experience
greater electrostatic forces of attraction.
[1]
2Rb+(g) + O2(g)

[1]

c G = H T S; 267/0.172; 1552 K

iii (Measuring electrical) conductivity /


(measuring) pH.

Rb2O(s)

(2 80.9) + 249.2 + (2 403.0) 146.1 + 795.5 +


Hlattice (Rb2O) = 339.0

Hlattice (Rb2O) = 339.0 (1866.4) =


2205.4kJmol1
Hlattice (Rb2O) = 2205.4kJmol1[2]
d The ionic model is a good model for rubidium oxide
the bonds have very little covalent character. The
ionic model is not a good model for silver bromide
the bonds are polar covalent.
[2]
e The sodium ion is smaller than that of rubidium.
It can therefore approach the oxide ion more
closely and exert higher electrostatic forces of
attraction.[2]

b i

ii

Minimum/least/smallest energy needed (by


reactants/colliding particles) to react/start/
initiate a reaction

[1]

[1]

T1

[3]
Probability of molecules

3 a H = [394 + (558) (1219)] = +267kJmol1

T2

(Kinetic) energy

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 16


3 a i k = ln 2 / t = 0.693 / (1.62 104)
= 4.28 105s1[1]
ii ln k = ln A Ea/RT = ln 25 Ea/(8.31 1107)
Therefore: Ea/(8.31 1107) = ln 25 ln k
= ln 25 ln (4.28 105)
Ea = (8.31 1107)(ln 25 ln (4.27 105))
=122167Jmol1

Ea = +122.17kJmol1[2]

ii The pressure will decrease.


b i

17 Equilibrium
Paper 1
2 A

6 C

3 D

7 A

4 B

8 B

Paper 2

[HI]2
1 a Kc =
or Kc =
[H 2 ][I2 ]

4 a A; E

1.50 102
2

b i

7.5 103 0

Equilibrium: (7.5 103 x) (7.5 103 x) 2x


[HI]2
Therefore Kc =
[H 2 ][I2 ]

[2]

After 15 s (product) = 0.37 (moldm );


3

rate = 0.37moldm3 / 15s = 0.025moldm3s1[3]

ii At equilibrium/rates of forward and reverse


reactions are equal/G = 0.

2HI

Paper 1
1 C

11 D

Equilibrium concentrations: [H2] = [I2]


= 1.62 103moldm3

2 B

12 A

3 B

13 C

[HI] = 1.18 10 moldm

4 A

14 B

See pages 595 and 596 for examples of this


type of calculation

5 D

15 C

6 B

16 B

7 A

17 C

8 C

18 D

9 C

19 D

10 A

20 C

[4]

c Hydrogen bonding (dipoledipole interactions) and


London dispersion forces.
[1]
2

Change

Shift

Reason

Increase in
temperature

Equilibrium
position shift
to left

Since forward reaction


is exothermic (H is
negative)

Increase in
pressure

Equilibrium
position shift
to right

Since there are fewer


gas molecules on right
hand side

Addition of
catalyst to
mixture

No change in
equilibrium
position

A catalyst affects the


rate of forward and
reverse reactions equally

[1]

18 Acids and bases

(2x)2
53 =
(7.5 103 x)2

iv No effect on Kc (it just speeds up the


reaction).[1]

[1]

[H 2 ] 2 [I2 ] 2

Initial: 7.5 103

[1]

1.888
= 12.7
[1]
2
0.333 ( 0.667)
iii Side reactions or leaks in the system or not
operating under equilibrium conditions or
operating at a higher temperature or the
product might be collected before equilibrium
is reached.
[1]

H2 + I2

The temperature will increase.

Kc =

[HI]

b Initial [H2] = initial [I2] =


= 7.5 103 mol dm3

[1]

CO(g) + 2H2(g) CH3OH(g)


Initial amount: 1.00
2.00
0
Amount at
equilibrium/
mol:
1.00 0.85 2.00 1.70 0.85
[1]
Equilibrium
concentration: 0.15/0.45 0.30/0.45 0.85/0.45
[1]
= 0.333mol = 0.667mol = 1.889mol [1]

[1]

c Rate = k[NO2][F2][1]

5 D

[1]

ii

b Step 1 is the slowest step, therefore it has a higher


activation energy relative to step 2.
[2]

1 A

There will be no change in pressure.

ii The methanol concentration will increase. [1]


[CH 3 OH]
c i Kc =
[1]
[CO][H2 ]2

4 a Step 1 since it is the slowest.

3 a i

[3]

Paper 2
1 a i

pH = log [H+(aq)][1]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 17


ii The curve should include the following:
starting pH = 1; equivalence point: 25.0cm3
of NaOH; pH at equivalence point = 7; pH to
finish = 1213.
[4]

pH

13
7
1
25
Volume/cm3

iii Ka = 104.76 = 1.74 105 ;


Ka = [H+(aq)]2 [CH3COOH] / 1.74 105

[H+(aq)]2
=
0.100

[H+(aq)] = 1.32 103 (moldm3);

Starting pH = 2.88;

pH at equivalence point: 89

b i

[5]

HIn is a weak acid:


In acid the equilibrium moves to the left or vice
versa.[3]

ii Phenolphthalein / phenol red / bromothymol


blue; the colour change of indicator occurs
within the range of pH at the equivalence
point / on vertical part of graph.
[2]

c i

Specific examples of weak base and its salt /


specific strong acid and weak base, e.g. NH3
and NH4Cl.[1]

ii pH changes very little / most of the acid is


neutralized by base, for example:
NH3 + H+ NH4+ or
NH4OH + H+ NH4+ + H2O[2]

3 a Acidic because it is a hydrogen ion donor and


basic because it is a hydrogen ion acceptor. Such
substances are described as amphoteric.
[2]
b Oxide ion, O2.[1]
c pH is the negative logarithm to the base ten of the
hydrogen ion concentration. pH = log10[H+(aq)].
pH of pure water = 7
[2]
d i Kw = [H+(aq)] [OH(aq)][1]
ii Water is more dissociated or ionized at a higher
temperature. Le Chteliers principle implies
that endothermic reactions are favoured by
increases in temperature, hence the dissociation
or ionization of water is endothermic.
[3]

19 Redox processes
Paper 1
1 D

9 B

d BrnstedLowry acid is a proton donor; a Lewis


acid is an electron pair acceptor;
HI(g) + H2O(l) H3O+(aq) + I(aq);
N2H4(g) + H+(g) N2H5+(g)

2 C

10 B

3 B

11 B

4 C

12 A

e It will be acidic due to a hydrolysis reaction


between the aluminium ion and water molecules;
[Al(H2O)6]3+ [Al(H2O)5OH]2+ + H+(aq)

5 D

13 B

6 B

14 A

7 A

15 B

2 a A buffer solution is an aqueous solution that resists


a change in pH when a small amount of a strong
acid or base is added.

Hence, there is only a very small change in the


concentrations of HA and A. The strong acid (H+)
is replaced by a weak acid, HA.
[5]
7.2 g
b Amount of sodium benzoate =
144 g mol 1
= 0.05 mol

The calculation assumes that all of the anion
concentration is derived from the salt only (as that
from the acid is too small to consider). It also assumes
that the ionization of the acid is so small it can be
ignored. Standard conditions (1 atm and 298 K) are
also assumed.
[3]
+
[H
(aq)]

0.05
105moldm3 6.3 105 =
0.03
[H+(aq)] = 3.78 105moldm3

pH = log10[H+(aq)] = 4.42
[2]
c A weak acid is partially or incompletely ionized
or dissociated. A monoprotic acid donates one
hydrogen ion per molecule.
[2]

HIn H+ + In and two colours indicated:


A buffer contains a weak acid (HA) and its


conjugate base (A) or a weak base and its conjugate
acid.
If hydrogen ions, H+(aq), are added, these will
react with the base of the buffer. The hydrogen
ions are removed as they combine with A and the
equilibrium shifts to the left.

8 A

Paper 2
1 a Oxidation number of copper on left hand side is 0;
oxidation number of nitrogen on right hand side
is+5.[2]

Oxidation number of copper on right hand side is
+2; oxidation numbers of nitrogen on right hand
side are +5 and +2.
[2]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 18

3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 2NO(g)


+ 4H2O(l)[1]
b i

ClO(aq) + SO2(aq) + H2O(l)


SO 42 (aq) + 2H+(aq) + Cl(aq)

The two electrodes must be dipping into aqueous


solutions of their ions. The two electrodes must
be connected via a salt bridge and an external
circuit consisting of wire and a voltmeter.
[3]

ii Hydrogen gas at 1atm pressure passed over


a platinum electrode. The temperature of all
chemicals is 298K and all solutions have a
concentration of 1moldm3.[3]

ii

b i

c i Ni2+(aq) + 2e Ni(s); Mn(s) Mn2+(aq) + 2e[2]


Manganese is oxidized.

The electron flow is from manganese


to nickel.

[1]
[1]

Paper 1

G is negative.

[1]

1 C

6 A

2 D

7 B

3 A

8 D

4 A

9 C

5 C

10 C

[1]
[1]

2 a Cathode (negative electrode):


Cu(s) Cu2+(aq) + 2e[1]

Anode (positive electrode):


Cu2+(aq) + 2e Cu(s)

[1]

b There is no change in the intensity of colour since


the rate of removal of copper(ii) ions at the cathode
is balanced by the rate of formation of copper(ii)
ions at the anode.
[1]

20 Organic chemistry

[1]

Oxygen is formed at the anode


(positive electrode).

There is no change in the pH since hydrogen and


hydroxide ions are not involved in the discharge
reactions.[1]
c 2H2O(l) O2(g) + 4H+(aq) + 4e[2]
d Charge passed = 0.360A 600s = 216C

[1]

Amount of electrons = 216C 96500Cmol1

= 2.24 103mol

2 moles of electrons are required for the discharge of


one mole of copper atoms.
[1]

Mass of copper deposited


= 0.50 63.55gmol1 02.24 103mol = 0.071g [1]

3 a i ClO(aq) + 2H+(aq) + 2e
H2O(l) + Cl(aq)
SO 42(aq) + 4H+(aq) + 2e
SO2(aq) + 2H2O(l)

Accept SO 42 (aq) + 4H+(aq) + 2e


H2SO3(aq) + H2O(l)

For final equation

Final oxidation
number
I/1
+VI/+6

Potential (of reduction half-reaction) under


standard conditions measured relative to
standard hydrogen electrode/SHE.
[1]

iii Ecell = (0.23V) + (1.18V) = +0.95V


d Gold is formed at the cathode
(negative electrode).

Initial oxidation
Element number
Chlorine +I/+1
Sulfur
+IV/+4

ii Yes it is energetically feasible; would have a


positive Ecell/ chlorate(v) ion stronger oxidizing
agent than dichromate(vi) ion.
[2]

[1]

Manganese(ii) ions are the oxidizing agent. [1]


ii Manganese is the anode.

Accept ClO(aq) + H2SO4(aq)


SO 42 (aq) + 2H+(aq) + Cl(aq)[4]

[1]

Paper 2
1 a Mechanism showing: arrow from C=C double bond
towards I; arrow from ICl bond to Cl; carbocation
showing I on first carbon and positive charge on
second carbon; arrow from Cl to carbon with
positive charge and structure of product
(see page 686 for this type of mechanism).
[4]
b 1-Chloro-2-iodobutane / 2-iodo-1-chlorobutane;
formed via primary carbocation, which is less stable
than the secondary carbocation; free electronreleasing alkyl groups / positive charge spread
out less.
[3]
2 a Electrophilic substitution

[1]

b Mechanism showing: curly arrow from delocalized


electrons to Cl+; structure of intermediate showing Cl
attached to ring, positive charge and the remaining
four electrons in the benzene ring; curly arrow
showing CH bond fission and electrons moving
into benzene ring (see Figure 20.38b, page 689). [3]
c J: C6H5CH2Cl; K: C6H5CHCl2; L: C6H5CCl3[3]
d Free radical substitution

[1]

e Cl2 2Cl; sunlight / UV light

[2]

f C6H5CH2Cl + Cl C6H5CHCl + HCl


C6H5CHCl + Cl2 C6H5CHCl2 + Cl

[2]

g C6H5CCl2 + Cl C6H5CCl3[1]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 19


3 a i

Show structure with the Hs on the different


carbon atoms diagonally opposite each other
(the trans form).[1]

ii There is restricted rotation around the axis of


the carboncarbon double bond, so one form
cannot be transformed into the other / the
presence of the pi electron cloud makes the
molecule rigid.
[2]
iii Hex-2-ene

b i

Electrophilic addition

[1]
[1]

ii CH3CH2CHBrCH2CH2CH3; the third carbon


atom in the chain is a chiral centre as it has
four different substituents attached to it (note
that the alternative structure with the Br
attached to the second carbon atom is also
possible and also shows optical isomerism). [2]
iii Mechanism involving carbocation
formation (see page 686).

[4]

iv In this case there are two possible secondary


carbocations that could be formed and
Markovnikovs rule cannot distinguish between
them.[2]
4 a The isomers are: A 1-bromobutane;
B 2-bromobutane; C 2-bromo-2-methylpropane;
D 1-bromo-2-methylpropane.
[4]
b i C; SN1: Substitution/Nucleophilic/
unimolecular.[2]
ii RBr R+ + Br; heterolytic fission to form the
carbocation intermediate. 
[2]
iii A; see Figure 20.3, page 673.

[4]

c Mechanism b(i): no change in rate; mechanism


b(iii): rate doubles.
[2]
d The rate of reaction with 1-bromobutane is
faster than for 1-chlorobutane as the CBr bond
is weaker than the CCl bond; Br is a better
leaving group than Cl.[2]
e B shows optical isomerism as the molecule contains
a carbon atom with four different groups attached.
Solutions of the two isomers will rotate the plane
of plane-polarized light in opposite directions and
this is detected in a polarimeter (see page 709).
The polarimeter is set up with water to align the
filters to obtain maximum extinction of light.
The solutions of the two isomers of the same
concentration are then tested one will rotate the
plane to the right, the other to the left by the same
amount. The physical and chemical properties of
the two isomers are the same.
[5]
5 In each case decide the priority of the different groups
attached to the carbon atoms making the carbon
carbon double bond
A is the E-isomer as the high priority groups are on
different sides of the molecule (different carbon atoms
of the two forming the double bond).

B is the E-isomer as the high priority groups are on


different sides of the molecule.

C is the Z-isomer as the high priority groups are on the


same side of the molecule (attached to the same carbon
atom of the two forming the double bond).
[9]

Chapter 21 Measurement and


analysis
Paper 1
1 A

4 A

2 C

5 D

3 B

6 D

Paper 2
1 a There is a stationary phase and a mobile phase. [1]

The components of the mixture dissolve, absorb,


or partition to differing extents between the two
phases.[1]

b i A

[1]

ii B

[1]

iii No, the two oranges are different substances


[2]
since they have different Rf values.
9
= 0.41
[1]
iv Rf value =
22
1.6
= 0.13
[1]
c i Rf value of compound 1 =
12.6
9.2
= 0.73
[1]
Rf value of compound 2 =
12.6

Compound 1 has a greater affinity for the thin


layer than compound 2. Since the thin layer
is composed of silica gel, compound 1 is more
polar than compound 2.
[1]

ii TLC is faster than paper chromatography.


The thin layer may be made from a variety of
different solids. Hence, a range of mixtures can
be separated by using different stationary and
mobile phases.
[1]
2 a By measuring the difference in time between the
injection of the sample and the centre of the peak
for a component.
[1]
b The areas under the peaks represent the amounts of
the components in the mixture.
[1]
c i Hexan-1-ol
ii Ethanol

[1]
[1]

d Flow rate of the carrier gas; temperature of the


column; length and diameter of the column; the
nature of column surface and the volatility of the
solute.[1]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

 20


The two compounds have relatively high
melting points and are involatile.

ii HPLC.
3 a 3350cm1 due to OH bond; 2900cm1 due
to CH bond.

[2]
[1]
[2]

Award [1] if both bonds given but not linked to correct


absorption.
b Comparison of fingerprint regions/comparison with
library, database or known spectra.
[1]
c Same molecular ion/parent ion (M) due to
C4H9OH+/C4H10O+.[1]

4 It has four hydrogen environments and there will


be splitting of the methyl group and both sets of
methylene (CH2) protons. In the high resolution 1H
NMR spectrum the methyl group (CH3CH2CH2OH)
is a triplet at approximately 1 ppm and the alcohol or
hydroxyl group (CH3CH2CH2OH) is a broad singlet at
approximately 2.3 ppm. Of the two methylene groups,
the one next to the highly electronegative oxygen atom
of the OH group is most downfield at approximately
3.6 ppm. This methylene group (CH3CH2CH2OH) is
split into a triplet. The methylene group adjacent to the
methyl group appears as a sextet.

CH3CH2CH2OH

d i (m/z = 57) C4H9+ / (CH3)3C+.


ii (m/z = 45) C2H5O+ / CH3CHOH+ / C2H4OH+.[2]

Penalize missing charge once only in (c) and (d).


e i

Four peaks because four different hydrogen


environments/four different types of proton/
OWTTE; 6:2:1:1.
[2]

ii (CH3)3COH/more detailed formula.

[1]

2
1
3
5
4
Chemical shift/ppm

CH3CH2CH2OH

e i

OH
CH3CH2CH2OH

[5]

Chemistry for the IB Diploma Second Edition Christopher Talbot, Richard Harwood and Christopher Coates 2015

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