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Reg. No. 200710217Z

Foundation Question of Physical Chemistry


Stoichiometry
(a) Mole
1. The composition of an organic compound W is 54.54% C, 9.09% H and 36.37%
O
by
mass.
Given that its Mr is 88.0, what is the molecular formula of W?
2.

(a)

Define the term relative atomic mass.

(b) The 4 isotopes of lead occur in the following abundances:


Relative isotopic mass
% abundance

204.0072 206.0612
1.37

207.0552

26.3

208.0602
20.8

51.53
Use these data to calculate a value, to 1 decimal place, for the Ar of lead.

3.

J96 P3 Q3
Which of the following contains 1 mol of the stated particles?
A chlorine molecules in 35.5 g of chlorine gas
B electrons in 3.01 x 1023 hydrogen molecules
C hydrogen ions in 1 dm3 of 1 mol dm3 aqueous sulfuric acid
D oxygen atoms in 22.4 dm3 of oxygen gas at s.t.p

4.

In a laboratory exercise to determine the degree of hydration of hydrated


barium chloride, BaCl2.xH2O, the following results were obtained:
Mass of hydrated barium chloride, BaCl2.xH2O = 2.44 g;
Mass of anhydrous barium chloride, BaCl2 = 2.08 g
Use these results to calculate the
(
percentage of water of hydration and

[1]

a
)
(

correct formula of hydrated barium chloride.

[2]

5.

Oxygen and hydrogen react explosively to produce water.


(a) Write a balanced equation for the reaction.
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Reg. No. 200710217Z

(b) A mixture of 15.0 cm3 oxygen and 55.0 cm3 hydrogen is sparked
continuously at r.t.p.

Assuming that the reaction goes to

completion,
(i) what is the total final volume of the reaction mixture at the end of [2]
reaction?
(ii) what is the maximum theoretical decrease in volume?
6.

20 cm3 of a gaseous hydrocarbon A (CxHy) was exploded with an excess of [3]


oxygen. There was a contraction in volume of 50 cm 3. When the products
were treated with excess sodium hydroxide solution, there was a further
contraction of 60 cm3. All volumes are measured at r.t.p. Deduce the
molecular formula of A.

MCQ
1. The relative abundances of the isotopes of a sample of neon are shown in the
table below.
Relative Isotopic Mass
Relative Abundance

20
90.92

21
0.26

What is the relative atomic mass of neon in this sample?


A
20.16
B
20.17
C
20.18
D
2.

Boron occurs naturally as two isotopes,

10
5

B and

22
8.82
20.20 (

11
5

B.

11
5

What is the percentage of B atoms in a sample of naturally-occurring boron?


A
0.8 %
B
8.0 %
C
20 %
D
80 % (
)
How many molecules are there in 500 cm3 of oxygen under room conditions?
A
1.25 B
1.34 1022C
2.5 1022
D
3.0 1022(
)
22
10

4.
A
B
C
D
5.

In which of the following are there one mole of the stated particles?
electrons in 1 g of hydrogen gas
chlorine molecules in 35.5 g of chlorine gas
oxygen atoms in 22.4 dm3 of oxygen gas at s.t.p.
hydrogen ions in 1 dm3 of 1 mol dm3 aqueous sulfuric acid
An adult human, in general, has a daily diet of 1.80 kg of carbohydrate
(empirical formula CH2O). If all the carbonydrate eaten is digested and
oxidized, what is the mass of carbon dioxide produced by a person each day?
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A
6.

0.267 kg B

0.800 kg C

1.32 kg

2.64 kg

Bromine can be extracted from the Dead Sea and transported as a 50 %


solution (by mass) of calcium bromide. What is the mass of bromine, in g,
contained in 100 g of solution?
A

50 160
100 200

50 80
120

50 160
200

50 200
160

7.

When a mixture of 10 cm3 of oxygen and 50 cm3 of hydrogen is sparked


continuously, what is the maximum theoretical decrease in volume? All gas
volumes measured at s.t.p.
A
10 cm3 B
15 cm3
C
20 cm3
D
30 cm3

8.

In polluted air, the white paint pigment in older oil paintings turns black due to
the formation of lead(II) sulfide, PbS. A solution of hydrogen peroxide can be
used to restore the white colour.
PbS(s) + 4H2O2(aq)
black pigment

PbSO4(s) +
white pigment

4H2O(l)

What is the mass of hydrogen peroxide required to react with 0.120 g of lead(II)
sulfide?
A
0.017 g B
0.030 g C
0.068 g
D
0.478 g
Airbags fitted in most modern cars are inflated by the nitrogen gas liberated
when sodium azide, NaN3, decomposes.
2NaN3 3N2 + 2Na
What volume of N2 at r.t.p. will be produced by a typical drivers airbag
containing 50 g of NaN3?
A
9.2 dm3 B
13.9 dm3 C
27.7 dm3
D
72.0 dm3(
)
(b) Volumetric Analysis
1. A solid sample containing ammonium sulfate was warmed with 250 cm 3 of
0.800
mol
dm3
sodium hydroxide solution. After the evolution of ammonia had ceased, the
sodium hydroxide solution that remained was neutralised by 85.0 cm 3 of 0.500
mol dm3 hydrochloric acid solution.
(a Write balanced equations for the reactions between
)
(i) ammonium sulfate and NaOH.
(ii NaOH and HCl.
)
(b Calculate the number of moles of sodium hydroxide added to
)
ammonium sulfate.
(c Calculate the number of moles of sodium hydroxide reacted with
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)
(d
)
(e
)

hydrochloric acid.
Calculate the number of moles of sodium hydroxide reacted with
ammonium sulfate.
Calculate the mass of ammonium sulfate present in the sample.

(c) Redox Titrations


1.

The waste from an electroplating factory contains chromium in the form of


dichromate(VI) ions, Cr2O72. In order to remove chromium from the waste,
green vitriol, FeSO4.7H2O, was first added to reduce the dichromate(VI) ions to
chromium(III) ions, Cr3+, in the presence of an acid. The chromium(III) ions
formed were then precipitated as chromium(III) hydroxide.
(a
)
(b
)

Write a balanced equation for the reaction of Cr 2O72 and Fe2+ ions in
acidic medium.
Results from an analysis show that there are 1.50 x 10 4 moles of
dichromate(VI) ions in a
1.0 dm3 sample of the waste. Calculate the mass of green vitriol required in
the treatment of 1.0 dm3 of waste.

2. 9.85 g of iron(II) ammonium sulfate crystals, FeSO 4(NH4)2SO4.6H2O, were made


up to 250 cm3 of solution in dilute sulfuric acid. 25.0 cm3 of this solution reacted
completely with 24.75 cm3 of a KMnO4 solution.
(a
)
(b
)
(c
)
(d
)
(e
)

Calculate the number of moles of Fe2+ in 25.0 cm3 of the solution.


Calculate the number of moles of KMnO4 that reacted.
Calculate the concentration of KMnO4 solution in mol dm3 and g dm3.
What is the volume of water that should be added to 1.8 dm 3 of the KMnO4
solution to convert the concentration to exactly 0.0200 mol dm3?

In an experiment, 50.0 cm3 of a 0.100 mol dm3 solution of metallic salt,


MCl3, reacted exactly with 25.0 cm3 of 0.100 mol dm3 of aqueous
sodium sulfite. The half equation for the oxidation of sulfite ion is :
SO32 + H2O

SO42 + 2H+ + 2e

If the original oxidation number of the metal, M, in the salt was +3, what
would be the new oxidation number of the metal?
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3.

Write the balanced equation for the above redox reaction.

Advo Education Group Pte Ltd


Reg. No. 200710217Z

]
4.

25.0 cm of a solution of X2O5 of concentration 0.100 mol dm

is reduced

by sulfur dioxide to a lower oxidation state. Re-oxidation of the element


X to its original oxidation state required 50.0 cm 3 of 0.0200 mol dm3
acidified

potassium

manganate(VII)

solution.

Assuming

that

manganate(VII) ions are reduced to Mn2+, to what oxidation number was [3


]
X reduced by sulfur dioxide?

N09 P3 Q3(b)
When sodium is burned in air, a mixture of sodium oxide, Na 2O, and
sodium peroxide, Na2O2, is formed. The mixture reacts with water
according to the following equations.
Na2O + H2O 2NaOH
Na2O2 + 2H2O 2NaOH + H2O2
The following information will allow you to calculate the relative amounts
of the two oxides produced when sodium is burned.

The mixture obtained by burning a sample of sodium was


dissolved in distilled water and made up to 100 cm 3 to give
solution H.

A 25.0 cm3 portion of solution H was titrated with 0.100 mol dm3
HCl. 22.50 cm3 of acid was required to reach the end-point.
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The H2O2 content of solution H was found by titration of another [1


25.0 cm3 portion with 0.0200 mol dm3 KMnO4. 10.0 cm3 of KMnO4 ]
solution was required to reach the end-point.

(a) Using the results of the HCl titration, calculate the total amount in [2
moles of NaOH in 100 cm3 of solution H.
(b)

Using the results of the KMnO 4 titration, calculate the amount in

moles of H2O2 in 100 cm3 of solution H.

[3

(c)Hence, calculate the amount in moles of Na 2O and Na2O2 formed ]


during the burning of the sodium sample.
MCQ
1.

N2O4, a poisonous gas, can be disposed of safely by reaction with sodium


hydroxide.
N2O4 + 2NaOH NaNO3 + NaNO2 + H2O
What volume of 0.5 mol dm3 NaOH is required to dispose of 0.02 mol of N2O4?
A

12.5 cm3

40 cm3

80 cm3

Which of the reactions shows the greatest change in oxidation number of


nitrogen?
A
B
C
D

3.

4NH3 + 5O2 4NO + 6H2O


3NO2 + H2O 2HNO3 + NO
2NO + O2 2NO2
4NH3 + 6NO 5N2 + 6H2O

2009 TPJC Prelim Q2


Disproportionation reaction occurs when an element undergoes oxidation and
reduction simultaneously. Which of the following equation describes a
disproportionation reaction?
A chlorine in
3ClO
ClO3 + 2Cl
B
carbon in
2H2C2O4 2H2O + 2C + 2CO + 2O2
C
sulfur in
2FeSO4 Fe2O3 + SO2 + SO3
D
manganese in
2KMnO4 MnO2 + MnO + K2O + 2O2
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2.

8 cm3

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Reg. No. 200710217Z

4.

2008 JJC Prelim Q1


Potassium iodate(V) can be used as a standard in iodine-thiosulfate titrimetric
since it reacts with iodide ions according to the equation:
IO3(aq) + 5I(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)
How many moles of sodium thiosulfate, Na 2S2O3, is needed to react with the
iodine
produced
by
1 mole of iodate(V) ions?
A

5.

2008 AJC Prelim Q2


An aqueous solution contains 1 mole of S 2O32 ions and this reduces 4 moles of
Cl2 molecules to chloride ions. What is the sulfur-containing product of this
reaction?
A

6.

SO2

SO32

SO42

S4O62

2002 JJC Prelim Q19


30.0 cm3 of 0.0500 mol dm3 aqueous iron(II) sulfate is titrated against 0.0250
mol dm3 aqueous potassium manganate(VII) under certain conditions. It is
determined that exactly 20.0 cm3 of the manganate(VII) solution is required to
reach end-point. If the final oxidation state of iron is +3, what would be the
final oxidation state of manganese?
A

+2

+3

+4

+6

Atomic Structure
N02 P3 Q1(b)-(d)
Atoms or ions that contain the same number of electrons are called
isoelectronic. Those that contain the same number of neutrons are called
isotonic. Those that contain the same number of protons are called isotopic.
The rest of this question is concerned with various properties of the following
five ions.
31
15

V 3 ,

32
15

W 2 ,

32
16

X 2 ,

Y ,

31
15

35
17

(N.B. the symbols V, W, X, Y and Z are not the atomic symbols of the element
concerned.)
(a Which of the above ions are (i) isoelectronic,
(ii) isotonic,
(iii)
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2
.

isotopic?
Which of the above ions would be deflected most when a beam is passed
through an electric field?
Which of the above ions would be deflected least when a beam is passed
through an electric field?

For the negatively charged ion

31
15

P 2 , determine the number of

(a Protons
)
(b Neutrons
)

(f
)
(
g
)
(c Electrons
(
)
h
)
(d energy levels (shells) containing (i
)
electrons
)
(e energy
sub-levels
(subshells) (j
)
containing electrons
)

orbitals containing electrons


completely filled orbitals

partially filled orbitals

unpaired electrons
valence electrons

3.

Using the s, p, d, f notation and the electrons-in-boxes configuration, write the


ground state electronic configuration of
(a N atom
(e Cu atom
)
)
2+
(b Ca ion
(f Cr2+ ion
)
)
2
(c S ion
(
Co3+ ion
)
g
)
(d Ti atom
(h Ge atom
)
)

4.

State and explain which species in the following pairs has a larger radius.
(a lithium and sodium
(b magnesium ion and aluminium
)
)
ion

5.

The first seven successive ionisation energies for a Period 3 element are as
follows:
760
(a
)
(b
)

1600

3200

4400

16000

19800

23800

kJ mol1

Which group in the Periodic Table does the element belong to and suggest
an identity for the element.
Write the electronic configuration of the atom of the element using the s,
p, d, f notation.
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)
(b
)
(c
)

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Reg. No. 200710217Z

6
.

(a A sample of copper contains the two isotopes 63Cu and 65Cu only. An
)
experiment is conducted to find the relative atomic mass of this
sample and is found to be 63.9.
(i) Explain why the value found is not a whole number.
(ii Suggest why the relative atomic mass stated above differs from
[
)
the value obtained from the Periodic Table.
2]
(
When separate beams of 63Cu2+ and 127I are passed through an electric
b field as shown in the diagram, they behave differently. A beam of
)
neutrons has already been drawn.
neutron

source

(i)
(ii
)
(a
)
(b)
(c)

8.

127

[3
]

What is meant by the term first ionisation energy (IE)?

[1
]
Sketch a graph of the first IEs of the elements sodium to potassium
[1
against proton number.
]
Using the graph, explain the difference in the first IEs of the following pairs of
elements.
(i) Na and K
Hint: First assess whether IE
(ii Mg and Al
follows the general trend or
)
its one of the irregularities.
(ii Si and P
[6
i)
]
(i P and S
v)

The figure on the right shows the energy


required to remove eight electrons, one at a
time, from an atom of element Q.

Ionisation energy

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7.

Sketch and label on the diagram how beams of of 63Cu2+ and


are affected by the electric field.
Given that the angle of deflection of the Cu2+ beam is 7.0o,
calculate the angle of deflection of the I beam, correct to 1
decimal place.

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Reg. No. 200710217Z

(a
)

(i
)
(ii
)
(b (i
)
)

Explain which group in the Periodic


Table element Q belongs to.
Can Q be an element belonging to
[
Period 2?
Give your reason.
4]
Write separate equations to illustrate
the first and second ionisation
energies of Q.
1 2 3(ii 4 Explain
5 6 7why
8 the ionisation energies
) increase
with the increasing number
[3
no. of electrons
removed
of electrons being removed.
]

8.

(c
)

Why is the energy difference between


the removal of the 5th and 6th electrons
much larger than the energy difference
between the removal of the 4th and 5th [2
electrons?
]
(d Name one element that could be the [
)
element Q and write its full electronic 2]
configuration using the s,p,d,f notation.
Atomic radius /
nm

9.

(a
)
(b
)

Iron

0.116

Sulfur

0.104

Ionic radius / nm
0.076 (Fe2+)
0.064 (Fe3+)
0.184

Explain why the atomic radii of iron and sulfur are different from the ionic
radii of their respective ions.
Explain why the ionic radius of Fe3+ is smaller than that of Fe2+.
[3
]

MCQ
[2009 AJC Prelim P1 Q3]
Gallium nitride, GaN, could revolutionise the design of electric light bulbs
because only a small length used as a filament gives excellent light at low
cost.
Gallium nitride is an ionic compound containing the Ga3+ ion.
What is the electronic configuration of the nitrogen ion in gallium nitride?
A
B

1s2 2s2
1s2 2s2 2p3

C
D

1s2 2s2 2p4


1s2 2s2 2p6

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Reg. No. 200710217Z

2.

[2003 Nov P1 Q4]


In 1999, Russian chemists claimed to be the first to identify atoms of a new
element of proton number 114. This was produced by bombarding atoms of
plutonium, Pu, with atoms of an isotope of Group II element, X. The reaction
taking place is the following.
244
94

Pu + X

289
114

+ 3 neutrons ( 10 n)

[new element]

What is X?
A
B

3.

Mg
Ca

C
D

Sr
Ba

[2003 Nov P1 Q3]


Oxygen reacts with platinum (VI) fluoride, PtF6, as follows.
O2 + PtF6

O 2 PtF 6
It was suggested that xenon should react similarly and, in this way, the first
noble gas compound was produced.
Xe + PtF6

Xe+PtF 6
What is the most likely reason for the suggestion being made?
A
B
C
D

[2008 SAJC Prelim P1 Q6]

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4.

O and Xe have similar atomic radii.


O and Xe have similar electron affinities.
O and Xe have similar electron configurations.
O2 and Xe have similar first ionisation energies.

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In an experiment, a sample was vaporised, ionised and passed through an


electric field. Analysis of the deflection occurring at the electric region
revealed the following data for the sample. It was observed that a beam of
Na+ gives an angle of deflection of 4.
Na+

Source

What are the possible identities of unknown particles, q and r, and the value
of ?
q
A
B
C
D

Be
Ba2+
Ba2+
Be2+

S2
S2
Br
Br

2.0
1.3
2.0
1.3

[2008 HCI Prelim Q3]


The variation in the second ionisation energy of six consecutive
elements in the Periodic Table is shown in the graph.
Which of these elements is a Group II element?

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5.

2+

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A
1, 2 and 3 are
correct

6.

B
1 and 2 only are
correct

C
2 and 3 only are
correct

D
1 only is
correct

Gaseous particle G and H have proton numbers n and (n+1) respectively. G


has a charge of +1 and H is isoelectronic with (has the same number of
electrons as) G.
Which of the following statements correctly describes G and H?
1
2
3

7.

The charge on G is half that on H.


G has a larger ionic radius than H.
G requires lesser energy than H when a further electron is removed
from each particle.

[2009 NJC Prelim P1 Q32]


(Use of the Data Booklet is relevant to this question.)
An ion X2 has 36 electrons and 45 neutrons. Which of the following
statements are true?
It is isoelectronic with Rb+.
It has a larger radius than Sr2+.
More energy is required to remove an electron from X than from X2.

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1
2
3

Chemical Bonding
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Explain the following observations.


(a
)
(b
)
(c
)

2
.

Magnesium chloride is soluble in water while ethene do not.

CO2
BCl3
PbCl4

(d
)
(e
)
(f)

SF6
SF4
SCl2

Al2O3
Al2Cl6
BeCl2

(d
)
(e
)
(f)

NO2

(g POCl3
)
(h SO32
)

N2O4
NO2

The table below gives some information on three chlorides that have similar
chemical formulae.
Formula of
chloride
XCl3
YCl3
ZCl3
(a
)
(b
)

5
.

(g PCl5
)
(h PCl3
)
(i ICl3
)

Draw the dot-and-cross of the following species.


(a
)
(b
)
(c
)

4
.

Aluminium metal is malleable while solid aluminium fluoride is brittle.

Draw and describe the shapes of the following molecules.


(a
)
(b
)
(c
)

3
.

Solid sodium conducts electricity while solid sodium chloride does not.

Molecular
Shape
Trigonal planar
Trigonal
pyramida
l
T-shape

Draw a dot-and-cross diagram of XCl3 & predict the Group to which


element X belongs.
Draw the stated shapes of YCl3 and ZCl3, and predict the Groups to which
elements Y & Z belong.

For each pair of substances, which one has a higher melting/boiling point?
Explain, in terms of structure and bonding.

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.

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(a
)
(b
)
(c
)
(d
)
(e
)
(f
)

Substance
A
NaCl

Substance
B
HCl

Substance A

Substance B

(g)

He

Ne

SiO2

SO2

(h)

CCl4

CF4

NaCl

MgO

(i)

CH3CH2CH2CH3

(CH3)3CH

Na

Al

(j)

CH3COCH3

CH3CH(OH)CH3

Ar

(k)

CHF3

CF4

H2O

H2S

(l)

Si

For (f), assume both species are of similar Mr.


6 N1996 P3 Q1
.
(a Draw 'dot-and-cross' diagrams for aluminium chloride and ammonia.
)
(b Explain why these two molecules form a product when they react in the
)
molar ratio 1:1.
(c By considering the number of bonding and non-bonding electron pairs,
)
draw diagrams to show the likely shapes of aluminium chloride, ammonia
and the product.
In your diagrams, clearly indicate the values of the bond angles.
While sulfur forms the compounds SF4 and SF6, no equivalent compounds
of oxygen, OF4 and OF6, are known. Suggest why this is so.
Caesium fluoride has a similar formula mass to SF6.
(i)
(ii
)

State the type of bonding in these two fluorides and suggest a reason
for the difference in their bonding.
Describe and explain three major differences you would expect to find
in the physical properties of the two fluorides.

State the type of hybridisation for each carbon


atom, C1 and C2, in the ethanoic acid molecule.
(ii) Sketch the shapes of the hybrid orbitals around
each atom C1 and C2.
(iii) Deduce the value of bond angles a, b and c.
(b) Carbon atom C2 can be described as being joined by
ethanoic acid
both a bond and a bond to one of the O atoms.
Briefly describe the terms in italics.
(c) In the vapour state, the Mr of ethanoic acid was found
to be 120. However, when ethanoic acid was
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dissolved in water, its Mr was 60. With the aid of a
diagram, explain
exhibited
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ethanoic acid.

8.

(a) (i)

Page21

7 (a
. )
(b
)

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Reg. No. 200710217Z

MCQ
1.

Which of the following pairs of substances consists of only giant structures?


A
B
C
D

2.
A
B
C
D
3.

aluminum and silicon(IV) oxide


aluminium oxide and aluminium chloride
silicon and chlorine
silicon and silicon(IV) chloride
Silicon carbide (carborundum) is a shiny, hard, chemically inert material with a
very high melting point. It can be used to sharpen knives and make crucibles.
Which type of structure explains these properties?
A giant structure with covalent bonds between silicon and carbon atoms.
A giant structure containing metallic bonding.
A giant layer structure with covalent bonds between atoms and van der
Waals forces between the layers.
A simple molecular structure with covalent bonds between the atoms of
silicon and carbon.
How many and bonds are present in the molecule on the right?

A
B
C
D
4.

Which isomer of the hydrocarbon C6H14 is likely to have the highest boiling
point?
A
B

6.

(CH3)3CCH2CH3
CH3CH2CH(CH3)CH2CH3

C
D

(CH3)2CHCH(CH3)2
CH3CH2CH2CH2CH2CH3

Which of the following molecules has no permanent dipole?


A

CBr2F2

CHF3

C2F4

C2H5Br

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5.

5
2
5
3
6
2
7
1
A compound has the structure as shown.

What are the values


of the bond angles , ,
and ?

A
104.5
120
107
B
107
180
104.5
C
107
120
104.5
D
104.5
90
107

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7.

Which of the following statements cannot be explained by hydrogen


bonding?
Ice has a density lower than water at 0 oC.
The boiling point of 2-nitrophenol is lower than that of 4-nitrophenol.
The boiling point of ethanal is higher than dimethyl ether, CH3OCH3.
The relative molecular mass of ethanoic acid is 120 when dissolved in
benzene.

A
B
C
D

The Gaseous State


1.

(a
)
(
b
)

State the two assumptions of the kinetic theory of gases that do not apply
for a real gas.
Under what conditions does a real gas behave most like an ideal gas?
Explain why.

2.

N04/P3/Q1(c)
Krypton reacts with fluorine to form a gas fluoride A. A mass of 0.100 g of
A occupies 104 cm3 at 2.00 104 Pa and 305 K. Calculate the relative
molecular mass of A, and hence suggest its formula.

3.

N06/P1/Q6

4.

Given a fixed amount of an ideal gas, sketch a graph for the following:
(a pressure (p) versus volume (V), under constant temperature
)
(
pressure (p) versus temperature (T/K), under constant volume
b
)
(c pressure (p) versus temperature (T/C), under constant volume
)
(
d pressure (p) versus 1V , under constant temperature
)
(e
pV versus volume (V), under constant temperature
)
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Page21

Flask X contains 1 dm3 of helium at 2 kPa and flask Y contains 2 dm3 of


neon at 1 kPa. If the flasks are connected at constant temperature and the
gases are allowed to mix, what is the final pressure in the flasks?

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(f
)

pV
versus pressure (p), under constant temperature
RT

Chemical Energetics (Part I : Enthalpy change of reaction)


Write balanced equation to represent the following enthalpy changes:
(a
)
(b
)
(c
)
(d
)
2
.

standard enthalpy change of formation of aqueous magnesium hydroxide


standard enthalpy change of combustion of ethane
lattice energy of lithium oxide

Name the enthalpy changes represented by the following equations.


(a
)
(b
)
(c
)
(d
)
(e
)

3
.

standard enthalpy change of formation of solid magnesium oxide

Na(s) + Cl2(g) NaCl(s)


Br2(l) Br(g)
Br2(g) 2Br(g)
CaF2(s) Ca2+(aq) + 2F(aq)
K+(g) K+(aq)

State whether the following enthalpies are exothermic or endothermic.


(a
)
(b
)
(c
)
(d
)
(e
)
(f
)
(g
)

enthalpy change of atomisation


lattice energy
enthalpy of combustion
enthalpy change neutralisation
enthalpy change of hydration
bond energy
ionisation energies
Page21

1
.

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4
.

Given: Hc of C(graphite) = 394 kJ mol1, Hc of H2(g) = 286 kJ mol1.


Calculate
(a) Hf of C2H2(g)
if Hc of C2H2(g) = 1300 kJ mol1
(b) Hf of C3H7OH(l)
if Hc of C3H7OH(l) = 2010 kJ mol1
(c) Hc of C6H12(l)
if Hf of C6H12(l) = 152 kJ mol1

5
.

(a Using appropriate data in the Data Booklet, calculate the standard


)
enthalpy change for the following reaction:
CH 3CH3(g) + Cl2(g)
CH3CH2Cl(g) + HCl(g)
(b This calculated value differs from the accurate value of +423 kJ mol 1.
)
Explain why.

6
.

The figure below shows a diagram of the apparatus used by a student to


determine the enthalpy change of combustion of ethanol. The heat produced
by the burning fuel warms a known mass of water. By measuring the mass of
fuel burnt and the temperature rise of the water, it is possible to obtain an
approximate value for the enthalpy change of combustion of the fuel.

(
a
)
(b
)

=
=
=
=
=

400 cm3
12.0 C
22.0 C
0.92 g
4.2 J g1 K1

Define the term standard enthalpy change of


combustion of liquid ethanol.

Calculate the enthalpy change of combustion of


liquid ethanol using the experimental data
given.
(c) An accurate value for HC(C2H5OH) is 1368 kJ
mol1. Suggest four serious errors in the simple
experiment which could be responsible for the
poor results.
7.

Thermometer
Metal calorimeter
Water

Improvised
spirit lamp
Ethanol

30.0 cm3 of 1.0 mol dm3 NaOH and 30.0 cm3 of 1.0 mol dm3 CH3COOH were
mixed in a polystyrene cup. The initial temperature of NaOH and CH 3COOH
and the highest temperature reached of the resulting mixture were recorded.
initial
temperature
of : 29.0
NaOH
C
initial
temperature
of : 29.4
CH3COOH
C
highest
temperature : 35.8
reached
C
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Volume of water in the calorimeter


Initial temperature of water
Final temperature of water
Mass of ethanol burnt
Specific heat capacity of water

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If 4.2 J are required to raise the temperature of 1 cm3 of solution by 1 C,

(a
)
(
b
)
8.

calculate the enthalpy change of neutralisation of CH3COOH with NaOH.


The enthalpy change of neutralisation of HCl with NaOH is 57.3 kJ mol1.
Compare your answer in (a) with the enthalpy change of neutralisation of
HCl with NaOH and suggest a possible reason for any difference.

The lattice energy of calcium fluoride can be calculated from a BornHaber


cycle using the following data:
H / kJ mol
1

enthalpy change of atomisation of


+178
calcium
enthalpy change of atomisation of
+79
fluorine
electron affinity of fluorine
328
enthalpy change of formation of
1220
calcium fluoride
(a Using the given data above and appropriate date in the Data Booklet,
)
calculate the lattice energy of calcium fluoride.
(
Explain how you would expect the numerical magnitude of the lattice
b energy of calcium fluoride to compare with that of
)
CaCl2(s)
CaO(s)
J1997 P2 Q2 modified
(a By means of a balanced chemical equation, including state symbols,
)
illustrate the term the average SiCl bond energy in SiCl4.
(b The standard enthalpy change of formation of SiCl4(g) is 610 kJ mol1.
)
The standard enthalpy changes of atomisation of silicon and chlorine are
+338 and +122 kJ mol1 respectively.
(i) Incorporate these three values into an energy cycle on an energy
level diagram.
(ii Hence calculate the average bond energy of the SiCl bond from
)
these data.

10. (a Using the data provided below, construct an energy cycle to represent the
)
solution of anhydrous magnesium chloride in a large volume of water and
thus determine the standard enthalpy change of solution of anhydrous
magnesium chloride.
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9.

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Lattice energy of MgCl2 = 2526 kJ mol1


Standard enthalpy change of hydration of Mg2+ = 1890 kJ mol1
Standard enthalpy change of hydration of Cl = 384 kJ mol1
(
b
)

Suggest and explain how you would expect the numerical value of the
enthalpy change of hydration of Ca2+ to compare with that of Mg2+.

MCQs
11
.

[N04/P1/Q8]
Some enthalpy changes of combustion are given below.
Hc / kJ
mol1
CO(g) + O2(g) CO2(g)

283

H2(g) + O2(g) H2O(l)

286

CH3OH(l) + 1O2(g) CO2(g) +


2H2O(l)

715

What is the enthalpy change of the following reaction?


CO(g) + 2H2(g) CH3OH(l)
A
C

140 kJ mol1

+ 140 kJ mol1

+ 146 kJ mol1

[N06/P1/Q7]
The heat liberated in the neutralisation given below is 114 kJ mol1.
2NaOH(aq) + H2SO4(aq) Na2SO4(aq) + 2H2O(l)
By using this information, what is the most likely value for the heat
liberated in the following neutralisation?
Ba(OH)2(aq) + 2HCl(aq) BaCl2(aq) + 2H2O(l)
A

57 kJ mol1

76 kJ mol1

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12
.

146 kJ mol1

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Reg. No. 200710217Z

114 kJ mol1

C
13
.

228 kJ mol1

[N08/P1/Q9]
For which process is the enthalpy change always negative?
A
B
C
D

14
.

burning an element in oxygen


dissolving a compound in water
forming an ion from an atom
synthesising a compound from its elements

[J96/P3/Q7, N01/P3/Q9]
Which statement helps to explain why calcium and chlorine form CaCl2
rather than CaCl?
Less energy is required to remove one electron from the calcium atom
than to remove two electrons.

More energy is released in forming chloride ions from chlorine


molecules in the formation of CaCl2(s) than in the formation of CaCl(s).

The lattice energy of CaCl(s) is less exothermic than that of CaCl2(s).

When CaCl(s) is formed from its elements, more energy is released than
when CaCl2(s) is formed from its elements.

[N98/P3/Q8]
The radius and charge of each six ions are shown in the table.
Ion
radius
nm

J+

L+

M2+

0.14

0.18

0.15

X
0.1
4

Y
0.18

Z 2
0.15

The ionic solids JX, LY and MZ are of the same lattice type.
What is the correct order of their lattice energies placing the one with the
highest numerical value first?
A

JX

>

LY

>

LY

>

>

M
Z

>

M
Z
JX

M
Z
JX

>

LY
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15
.

Advo Education Group Pte Ltd


Reg. No. 200710217Z

16
.

M
Z

>

LY

>

JX

[N05/P1/Q7]
The enthalpy change of solution of magnesium fluoride is negative (17.7 kJ
mol1), but the enthalpy change of solution of barium fluoride is positive
(+3.8 kJ mol1).
Which conclusion can be drawn from these data?
Magnesium fluoride is soluble in water, but barium fluoride is insoluble.

The hydration energy of the barium ion is numerically greater than that
of the magnesium ion.

The lattice energy of barium fluoride is numerically greater than that of


magnesium fluoride.

The lattice energy of barium fluoride is numerically greater than the


sum of the hydration energies of the barium and fluoride ions.

[N06/P1/Q33]
The conversion of graphite into diamond is an endothermic reaction (H =
+3 kJ mol1).
C (graphite) C (diamond)
Which statements are correct?
1

The enthalpy change of atomisation of diamond is smaller than that of


graphite.

The bond energy of the CC bonds in graphite is greater than that in


diamond.

The enthalpy change of combustion of diamond is greater than that of


graphite.

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17
.

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Chemical Energetics (Part II : Entropy change of reaction)


18 (a Explain what is meant by the term entropy of a chemical system.
. )
(
Predict and explain the sign of S for each of the following processes.
b
)
(i Na(s) Na(g)
)
(ii 2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g)
)
(iii Cl2(g) + 1 I2(s) 2 ICl3(l)
3
3
)
(iv 1 mol of Cl2(g) is added to 1 mol of N2(g)
)
(v) 1 mol of Cl2(g) at 298 K is heated to 373 K
19 Aluminium fluoride is made industrially by reacting aluminium oxide with
. hydrogen fluoride at a high temperature.
Al2O3(s) + 6HF(g)
2AlF3(s) + 3H2O(g)
(a Calculate the standard enthalpy change for the reaction, H, using the
)
following Hf values at 298 K.
compound
Hf / kJ mol1
Al2O3
1676
HF(g)
271
AlF3
1504
H2O(g)
242
The standard entropy change for this reaction, S, is 390 J mol1.
(b Explain the significance of the sign of S.
)

(c Use this value of S and the H you obtained in (a) to calculate the G at
298 K.
)
(d How will the value of G for this reaction change with temperature, and
)
what consequences will this have for the conditions used to make AlF3
industrially?
N2008/II/2 (b) & (c)
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20
.

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Silver forms a series of halides of general formula AgX. The chloride,


bromide and iodide of silver are sparingly soluble in water at room
temperature.
Data about the solubilities in water and the solubility products of the
chloride, bromide and iodide of silver at 298K are given below.
Salt
AgCl
AgBr
AgI

Solubility /
1.4
7.1
8.9

mol dm3
105
107
109

Solubility product / mol2 dm6


2.0 1010
5.4 1015
8.0 1017

(a When a precipitate is formed, Gppt , in J mol1, is given by the


)
following expression.
Gppt = 2.303RT log Ksp
20
.

Use the data above to calculate Gppt, in kJ mol1, for silver


chloride.
(ii The standard enthalpy change of formation of the
)
precipitate AgCl(s) is
66.0 kJ mol1. Use your answer in (i) to calculate Sppt, in J
mol1 K1, for the formation of the precipitate AgCl(s) at 298
K.
(iii Explain the significance of the sign of your answer in (ii)
)
(b For silver fluoride, AgF, Ksp = 1.006 mol2 dm6 at 298 K.
)
Use the expression given in (a) to determine whether silver
fluoride is soluble in water at 298 K. Explain your answer.
(a (i)
)

[2
]

[2
]
[1
]
[2
]

Chemical Eqm
CO2(g) + H2(g) CO(g) + H2O(g)
Equilibrium partial pressure/ atm
20
9
15
20
(a Write an expression for the equilibrium constant, Kp in terms of partial
)
pressures and determine its value.
(
What would be the new equilibrium partial pressure of CO 2(g) when the
b partial pressure of H2(g) is increased to 20 atm?
)
A
9 atm
B between 9 & 20 atm
C 20 atm
D between 20
and 29 atm

2 For the reaction below, 2X2(g) + Y2(g) 2X2Y(g), the value of the equilibrium
.
constant Kc is 5.
Determine the Kc values for the following equilibria, including its units.
(a

4X2(g) + 2Y2(g)

4X2Y(g)
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Reg. No. 200710217Z

)
(b
)
3
.

X2Y(g)

X2(g) + Y2(g)

(a State the Le Chaterliers Principle.


)
(b Consider the reaction :
)
N2(g) + 3H2(g)
2NH3(g)
H = 92.6 kJmol1
State, with reasons, how the equilibrium position and equilibrium constant
will be affected due to the following changes :

4
.

State and explain whether the forward reaction is endothermic or exothermic,


given that Kc of a reaction increases with temperature.

5
.

The key stage in the manufacture of sulfuric acid is the reaction between sulfur
dioxide and oxygen.
2 SO2(g) + O2(g)
2 SO3(g)
When a 2:1 mixture of SO 2 and O2 was allowed to reach equilibrium at 500 C
and a total pressure of 5 atm, the partial pressure of SO 3 was found to be 4.7
atm.
(a (i) Write an expression for Kp for this reaction, giving its units.
)
(ii Calculate the value for Kp at 500 C.
)
(b The same reaction is repeated with a 2:1 mixture of SO 2 and O2 at a total
)
initial pressure of 3 atm and passed over a catalyst at 430 C, the partial
pressure of SO3 at equilibrium is found to be 1.9 atm.
(i) Calculate the partial pressure of SO2 and O2 at equilibrium.
(ii Hence, calculate the new total pressure and the % conversion of SO 2
)
into SO3.
(iii Calculate the value for Kp at 430 C.
)
(c By comparing your answer in (a)(ii) and (b)(iii), state and explain if the
)
above reaction is endothermic or exothermic.
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(i) a decrease in volume of system,


(ii) an increase in the temperature,
(iii addition of iron catalyst.
)

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6. [N2006 P3 Q3 either]
When the gases dinitrogen tetroxide and nitrogen monoxide are mixed in a 1:2
ratio, the two gases slowly react to form the blue compound dinitrogen trioxide
according to the following equilibrium.
N2O4(g) + 2NO(g)
2N2O3(g);
H = 26 kJ mol1
(a
)
(b
)

(b
)
(c
)

Draw a sketch graph showing how the rates of the forward and reverse
reactions change from the time the two gases are mixed to the time the
reaction reaches equilibrium. Label your two lines clearly.
A mixture containing a 1:2 ratio of N 2O4 and NO at an initial total pressure
of 3 atm was allowed to reach equilibrium. At equilibrium the following
partial pressures were measured.
compound
partial pressure /
atm
N2O4
0.75
NO
1.50
N2O3
0.25
(i) Write the expression for Kp, including its units.
(ii) Calculate a value for Kp.
Suggest, with an explanation, how the position of equilibrium
might alter when
(i) the temperature is increased,
(ii) the pressure is increased.

(i)
(ii)

(iii
)

Write an expression for Kc for this reaction, stating its units.


Experiments have shown that when the [O2] = 7.6 x 106 mol
dm3, the concentrations of Hb and Hb(O2)4 are equal.
Use this information to calculate a value for Kc.
Use your value of Kc to calculate the [O2] necessary for 99%
of the Hb to be converted to Hb(O2)4.
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[6

Page21

7. [N2009 P3 Q1c,d]
(a One molecule of haemoglobin can bind up to four molecules of
)
oxygen, according to the following equation.
Hb(aq) + 4O2(aq)
Hb(O2)4(aq)

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Reg. No. 200710217Z

]
(b
)

Myoglobin, Mb, is an oxygen-carrier protein that occurs in muscle


fibres. It has a higher affinity for O2 than does Hb, but only binds
one O2 molecule per Mb molecule.
Mb(aq) + O2(aq)
MbO2(aq)
Kc = 1 x 106 mol dm3
Calculate the percentage of MbO2 in an Mb-MbO2 mixture when
[O2] = 7.6 x 106 mol dm3.

[2
]

8. [N2002 P3 Q3 modified]
The equilibrium mixture in a 2 litre vessel at 773 K and 1.3 atm
contains 0.60 mol of sulfur dioxide, 0.20 mol of oxygen and 4.80 mol of
sulfur trioxide.
2SO2(g) + O2(g)
(a
)
(b
)

8. (c)

2SO3(g)

H = 197 kJ mol1

Calculate the equilibrium constants (i) Kc and (ii) Kp .


Calculate the amount of O2 that must be added to increase the
amount of SO3 at equilibrium to 5.0 mol.

[4
]
[3
]

Complete the graph below, when the calculated amount of O2 in


part (b) is added to the above equilibrium mixture at time t.

Page21

4.80

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0.60
0.20

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Amount

SO3

SO2
O2

time

t1

MCQ
9.

[N2008 P1 Q7]

10 [N2009 P1 Q12]
.
11 [N2010 P1 Q13]
.
12 [N2008 P1 Q12 modified]
.
Which statement is correct about a reaction for which the equilibrium
constant is independent of temperature?
A
When temperature rises, the position of equilibrium is changed.
B
The rates for both forward and reverse reactions are equal.
C
The enthalpy change for the reaction is zero.
D
There are equal numbers of moles of reactants and products.
13 [2009 AJC P1 Q12]
.
The graphs below show how the percentage of gaseous products present at
equilibrium vary with temperature and pressure.

(T + 10) oC
T oC
pressure
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% products
at equilibrium

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Reg. No. 200710217Z

Which one of the following reactions could the graph represent?


A
H2(g) + I2(g) 2HI(g)
H = +53 kJ mol1
B
N2(g) + 3H2(g) 2NH3(g)
H = 92 kJ mol1
C
N2O4(g) 2NO2(g)
H = +57 kJ mol1
D

2Fe(s) +

3
O2(g)
2

Fe2O3(s)

H = 822 kJ mol1

Ionic Equilibrium

2.

(a
)
(b
)

Define Kw and explain why, at 25 C, water has a pH of 7.

(a
)
(b
)

What do you understand by the BronstedLowry theory of acids and


bases?
Water can react as either and acid or a base. Construct balanced
equations to show how water can act as a Bronsted base or a Bronsted
acid when reacting with :
(i) Ammonia
(ii) hydrochloric acid
Given that ionic product of water is 1.0010 14 mol2 dm6 at 25 C,
calculate the pH of the following solution.
Ka for ethanoic acid = 1.80 105 mol dm3
Kb for ammonia = 1.78 105 mol dm3
(i) 0.0500 mol dm3 hydrochloric acid
(ii 0.0170 mol dm3 sodium hydroxide
)
(iii 0.0500 mol dm3 ethanoic acid
)
(iv 0.0170 mol dm3 aqueous ammonia
)
(v) 0.690 mol dm3 sodium ethanoate,
(vi 0.750 mol dm3 ammonium chloride
)

State and explain how the value of Kw varies with temperature.

(c
)

3. The
(a
)
(b
)

dissociation constant for ethanoic acid, Ka, is 1.8 105 mol dm3.
Calculate the pH of a 0.100 mol dm3 solution of ethanoic acid.
Sketch the pH-volume added curve you would expect to obtain when 30
cm3
of
3
3
0.100 mol dm sodium hydroxide is added to a 10.0 cm of 0.100 mol dm3
ethanoic acid.
Mark clearly the equivalence point and the point at which pH = pKa.
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Reg. No. 200710217Z

(c
)

Suggest a suitable indicator from the following list and state the colour
change at end-point.
Indicator
pH at which
Colour of
Colour of
colour changes
acid form
base form
methyl yellow
2.9 4.0
Red
Yellow
bromothymol
6.0 7.6
blue
Yellow
Blue
thymol blue
8.0 9.6
Yellow
Blue

4. [J2002 P4 Q1 modified]
(a Write an expression for Kw.
)
(b Use your expression to help you calculate the pH of 0.200 mol dm3
)
NaOH(aq).
(c The pH of 0.200 mol dm3 NH3(aq) is 11.3. Explain why this answer differs
)
from your answer in (b).
(d Sketch the pH-volume added curve you would expect to obtain when 60
)
cm3
of
0.100 mol dm-3 HCl(aq) is added to a 20.0 cm3 of 0.200 mol dm3 NH3(aq).
Mark clearly the equivalence point and the point of maximum buffering
capacity.
(e Mixtures of basic amines and its salts can act as buffer solutions, resisting
)
changes in pH when acids or alkalis are added.
Explain, with the help of equations, how a CH 3NH2(aq) CH3NH3Cl(aq)
mixture acts as a buffer.
5 The water of Lake Nakuru in the Kenyan rift valley contains dissolved sodium
. carbonate and sodium hydrogen carbonate. The following equilibrium exists :
HCO3 (aq)
H+ (aq) + CO32 (aq)
(a) (i) What do you understand by the term buffer?
(ii With the aid of equations, explain how this solution acts as a buffer
)
on the addition of either acid or base.
(b)

CO32
The pH of Lake Nakuru is 10.3 and the ratio
is 0.958. Calculate the
HCO3

6 For each of the following, write the expression of Ksp and calculate its value.
.
(a The solubility of silver chloride in water is 1.15 105 mol dm3 at 25 C.
)
(b The solubility of lead(II) chloride in water is 0.0200 mol dm3 at 25 C.
)
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equilibrium constant for the above reaction.

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7 For
.
(a
)
(b
)
(c)

each of the following, calculate the solubility, in mol dm3, of


zinc hydroxide in water, given Ksp of zinc hydroxide = 4.51017 mol3 dm9.
zinc hydroxide in 0.01 mol dm3 of NaOH(aq) solution.
Account for the difference in the solubility of zinc hydroxide calculated in
(a) and (b).

8 For each of the following, predict if precipitate will be formed. Show your
. workings clearly.
(a Equal volume of 1.2105 mol dm3 AgNO3(aq) and 3.0105 mol dm3
)
NaBr(aq).
(Ksp of AgBr = 7.71013 mol2 dm6)
(b 10 cm3 of 0.100 mol dm3 Zn(NO3)2(aq) and 40 cm3 of 0.00100 mol dm3
)
NaOH(aq).
(Ksp of Zn(OH)2 = 4.51017 mol3 dm9)

Reaction Kinetics
The following results were obtained for the reaction A + B + 3C D.
Expt
No.

Initial
Initial [B]/
Initial
Initial rate of formation
[A]/ mol
mol dm-3 [C]/ mol
of D
-3
-3
dm
dm
/ mol dm3 min1
1
0.1
0.2
0.3
9.0 x 105
2
0.3
0.5
0.3
8.1 x 104
3
0.1
0.3
0.3
9.0 x 105
4
0.1
0.4
0.9
2.7 x 104
(a What is the order of reaction with respect to (i) [A]
(ii) [B]
(iii)
)
[C]?
(b Write the rate equation for the reaction. Calculate the rate constant and
)
state its units.

Page21

1
.

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The graph below shows the concentration of iodine remaining after a given
time when iodine is allowed to react with propanone in acidified aqueous
solution. Propanone and H+ are used in large excess compared with I2.
Two experiments were carried out at different concentrations of H + of 1.0 mol
dm3
and
3
2.0 mol dm respectively.

(a
)
(b
)
(c
)

3.

Explain clearly, with working, how the rate of reaction between I 2 and
propanone depends on
(i) [I2],
(ii) [H+].
The reaction is first order with respect to propanone. Write a rate equation
for the reaction.
Explain why propanone and H+ are used in large excess.

N1999 P1 Q2 modified

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.

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Ethyl ethanoate undergoes a slow acid-catalysed hydrolysis in water:


HCl

CH3 CO2CH2CH3 + H2O

CH3CO2H + CH3CH2OH

The reaction was followed twice with different concentrations of HCl and the
following results were obtained.
Time /
min

(b)
(c)
4
.

5.

The
first
(a
)
(b
)

rate of removal of the pain-killing drug, paracetamol, from the body is a


order reaction with a rate constant, k, of 0.26 hr-1.
Calculate the half-life of the removal of paracetamol from the body.
How many half-lives have passed when 6.25 % of the original dose of
paracetamol remains in the body? Hence determine the time taken for the
original dose of paracetamol to decrease to this amount.

Aqueous hydrogen peroxide decomposes readily in the presence of a catalyst


according to the equation:
2H2O2(aq) 2H2O(l) + O2(g)
The data below relates the rate of decomposition of aqueous hydrogen
peroxide to its concentration in otherwise identical conditions.
[H2O2] / mol dm3
0.08
0.14
0.20
0.28
4
3
Rate / 10 ( mol dm
0.45
0.80
1.15
1.60
1
s )
(a With the aid of a graph, deduce the order of reaction with respect to
)
hydrogen peroxide.
(b Use your graph to find the halflife and rate constant for the reaction.
)
(c How would halving the initial concentration of hydrogen peroxide affect
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(a)

With [HCl ] = 0.1 mol


With [HCl ] = 0.2 mol
3
dm , [ethyl
dm3, [ethyl
ethanoate] / mol dm3
ethanoate] / mol dm3
0
0.200
0.200
25
0.152
0.115
50
0.115
0.067
75
0.088
0.038
100
0.067
0.022
125
0.051
0.013
(i) Plot the graphs on the same axes and show that the reaction is first
order with respect to [ester]. Also, deduce the order of reaction with
respect to [HCl].
(ii Deduce the rate equation and calculate the rate constant, giving its
)
units.
The reaction was repeated using 0.400 mol dm 3 of ethyl ethanoate and
0.1 mol dm3 of HCl. Suggest the half-life of ethyl ethanoate.
Explain, in molecular terms, how an increase in temperature can affect
the rate of a reaction.

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the initial rate and the halflife of this reaction?


With a suitable diagram, explain how and why the presence of a catalyst
affects the rate of a chemical reaction.
Explain how manganese(IV) oxide acts as a heterogenous catalyst for this
reaction.

6.

The equation for the reaction between peroxodisulfate ion and iodide ion is
shown below.
S2O82(aq) + 2I(aq) 2SO42(aq) + I2(aq)
An excess of KI(aq) was added to a sample of Na 2S2O8(aq) and the kinetics of
the reaction was studied by measuring [I2(aq)] at various times. At the end of
the reaction, the concentration of I2(aq) was found to be 2.00 mol dm3.
time / min
0
5
10
15
20
25
30
0
0.70 1.16 1.45 1.65 1.77 1.85
[I2] / mol
dm3
(a Plot a suitable graph to show that the kinetics is first order.
)
(b Suggest an experimental method to determine the concentration of I2(aq)
)
in the reaction mixture at various times.
(c With the aid of equations, explain briefly how Fe 2+(aq) or Fe3+(aq) can act
)
as a homogeneous catalyst in this reaction.

7
.

The decomposition of gaseous dinitrogen pentoxide is represented by


2N2O5(g) 4NO2(g) + O2(g)
and is first order with respect to dinitrogen pentoxide.
(a Write down the rate equation for the decomposition.
)
(b A proposed mechanism for the reaction is made up of the following steps:
)
N2O5 N2O3 + O2(g)
I
N2O3 NO + NO2
II
NO + N2O5 3NO2(g)
III
From your rate equation in (a), which of the above steps would be
expected
to
be
the
rate-determining step.

8
.

The kinetics of the reaction


2NO(g) + Br2(g) 2NOBr(g)
H = 23 kJ mol1
is second order with respect to [NO] and first order with respect to [Br 2]. The
activation energy for this elementary reaction is +5.4 kJ mol1.
(a
)
(b
)
(c
)

Write the rate equation for the reaction and state the units of the rate
constant.
Sketch and label a reaction pathway diagram for the reaction showing all
relevant energy changes.
State and explain the effect of the following on the rate of the reaction.
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)
(d
)
(e
)

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Reg. No. 200710217Z

(i)
(ii
)

Increase in partial pressure of Br2


Reduce the volume of the vessel

9. Enzymes catalyse biological reactions involving specific substrates. Draw a


sketch to show how the rate of an enzyme-catalysed reaction changes with
increasing concentration of the substrate, and explain the shape of the sketch
at high concentrations of the substrate.

Electrochemistry
Part I : Electrolysis
1. A current of 5.00 A is passed through molten copper(II) chloride for 20.0
minutes between graphite electrodes.
(a Write equations for the reactions at cathode and anode.
)
(b Calculate the amount of electrons passed through the cell.
)
(c Calculate the mass of copper deposited.
)
(d Calculate the volume, measured at s.t.p, of the gas evolved.
)

3. 0.750 g of manganese is deposited on the cathode when a current of 1.00 A is


passed through a solution of manganesecontaining electrolyte for 1.1 hour.
(a Calculate the amount of manganese deposited.
)
(b Calculate the amount of electrons passed through the cell.
)
(c Hence, determine the oxidation state of manganese in the electrolyte.
)
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2. The mass of Pt cathode increased by 0.360 g after a current of 0.410 A had


passed through dilute AgNO3(aq) for 800 s.
(a Write equations for the reactions at cathode and anode.
)
(b Determine the amount of charge passed.
)
(c Obtain a value of the Faraday constant, F, from the above experimental
)
data.
(d Hence, determine a value of L, the Avogadro constant.
)

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4. Cell 1, containing aqueous silver nitrate, and Cell 2, containing aqueous


copper(II) sulfate, were connected in series. When a current was passed
through the circuit, 0.108 g of silver was deposited on an electrode in Cell 1.
(a Calculate the amount of electrons passed through the circuit.
)
(b Hence, determine the expected mass of copper deposited at the electrode
)
in Cell 2.
(c Suggest why the actual mass of copper deposited is likely to be less than
)
that in (b).
(d State how the mass of silver deposited varies with the following changes:
)
(i) current is halved,
(ii concentration of silver nitrate is doubled.
)
5. An object with a surface area of 1000 cm 2 is to be plated with silver of 2 10 3
cm in thickness.
(a Draw a labelled diagram of the electrical circuit for the electrolysis. In your
)
diagram, include the polarity of each electrode and the direction of
electron flow.
(b Given that a current of 5.00 A is applied, calculate the length of time, in
)
hours, required for the above electroplating to take place. (Density of silver
= 10.5 g cm3)

6. Using relevant data from the Data Booklet, explain how a sample of copper
containing zinc and silver impurities can be purified by electrolysis.

7. (a What do you understand by the term standard electrode potential.


)
(b Draw labelled diagrams to show how you could measure the standard
)
electrode potential of each of the following electrode systems. In your
diagram, indicate clearly the direction of electron flow in the external
circuit and polarity of the electrodes.
(i) Mg2+(aq)/Mg(s)
(ii Co3+/Co2+
(iii Cl2/Cl
)
)
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Part II : Galvanic Cell

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8. Electrical energy can be obtained from H2 and O2 gas in a fuel cell.


(a Write halfequations for the reaction occurring at the anode and cathode
)
using aqueous NaOH as the electrolyte.
(b Calculate the cell e.m.f if the process takes place under standard condition.
)
9. A cell consisting of a Cu 2+|Cu(s) halfcell and a Fe3+(aq), Fe2+(aq)|Pt(s) is shown
below.
V

Cu(s
)

1 mol dm
3
Cu2+
(aq) at
298K

(a
)
(b
)

Pt(s)
1 mol dm3 Fe2+
(aq)
1 mol dm3 Fe3+
(aq) at 298K

Predict the outcome of the above system with appropriate calculation.


Write a balanced equation for the reaction that occurs, if any.
State and explain how the cell potential will change when NaOH is added
to the oxidation
halfcell.

10 Using the E values in the Data Booklet, predict the reaction, if any, between
.
(a acidified dichromate(VI) ion and tin(II) ion
)
(b lead(IV) oxide and acidified aqueous hydrogen peroxide
)
(c) acidified potassium iodide and aqueous hydrogen peroxide
(d cobalt(II) ion and acidified manganate(VII) ion
)
(e zinc and tin(II) ion
)
(f) aqueous bromide ion and iron metal

N06/P2/Q2 modified
(a
)

Aqueous solutions of chlorine and iodine are added separately to


two test-tubes each containing Fe2+ ions. Aqueous sodium hydroxide
is then added to each tube. Results are given in the table below.
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1
1.

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Fe2+(aq)
after addition of
NaOH(aq)

Cl2(aq) added
I2(aq) added
green solution turns no
observable
yellow
change
brown precipitate
green precipitate

(i) What does the colour change when Cl2(aq) is added to Fe2+(aq)
indicate?

(b)

(ii
)

Use E values from the Data Booklet to explain your answer to


(i).

(ii
i)

[
Use E values to explain why there is no change when I2(aq) is
added to Fe2+(aq) and hence comment on the relative reactivity 6]
of Cl2 and I2 with Fe2+.

When aqueous potassium iodide is mixed with aqueous copper(II)


sulfate,
a
yellow-brown precipitate is formed and the solution loses its blue
colour. When the resulting mixture is shaken with hexane, a purple
layer is formed which floats on top of the mixture. A white solid, A,
with composition by mass: Cu, 33.3%; I, 66.7%, remains.
(i) Calculate the empirical formula of A.

(c
)

(ii
)

Determine the oxidation number of copper in A.

(ii
i)

What substance causes the purple colour when hexane is


added?

(i
Write an ionic equation, with state symbols, for the reaction of
[5
v) copper(II) sulfate with potassium iodide.
]
Standard redox potentials may be used to predict the feasibility of a
reaction.
(i) Use E values from the Data Booklet to show that reaction
between aqueous copper(II) sulfate and aqueous potassium
iodide is unlikely to occur.
By using your answers to (b)(iii) and (b)(iv), suggest one
[3
reason why this reaction does, in fact, occur.
]

Page21

(ii
)

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