2014 FY13CE Detailed Solutions Chemistry Paper 1 Modified

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MINISTRY OF EDUCATION
FIJI YEAR 13 CERTIFICATE EXAMINATION 2014
CHEMISTRY PAPER 1
QUESTIONS
AND
DETAILED SOLUTIONS
WITH
ADDITIONAL NOTES
© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

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SECTION A
For each Principal Quantum Number (n), the Secondary Quantum Number (l) can range from 0
to n-1.
Therefore for n = 3, l = 0, 1, 2.
3 refers to the shell, 0 refers to the s subshell, 1 refers to the p subshell and 2 refers to the d
subshell. Hence, for the third shell (n=3), only 3s, 3p and 3d subshells are possible.
For n = 7, l = 0, 1, 2, 3, 4, 5, 6 (7s, 7p, 7d, 7f, 7g, 7h,)

For n = 5, l = 0, 1, 2, 3, 4 (5s, 5p, 5d, 5f, 5g)
For n = 4, l = 0, 1, 2, 3 (4s, 4p, 4d, 4f)
Note the difference between shell, subshell and orbitals of an atom (For example the second shell
of an atom (n = 2):
Source: http://chemistry.stackexchange.com/questions/18466/difference-between-shells-subshells-and-orbitals

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According to the valence shell electron pair repulsion (VSEPR) theory, the force of repulsion
between lone pairs and bond pairs is not the same. The order of repulsion is as follows:
lone pair - lone pair > lone pair - bond pair > bond pair - bond pair
In ammonia (NH3), there are three bonded pair of electrons and one lone pair of electrons. The
repulsion between the lone pair of electrons and bonded pair is more than the repulsion between
the boned pairs. The shape of ammonia molecule is thus trigonal pyramidal, with bond angles of
107.5 ˚. In ammonium ion (NH4+), there are four bonded pair of electrons, with equal repulsion
between them. As such the four bonds are equally spaced around the nitrogen atom at 109.5˚,
assuming a tetrahedral shape.
trigonal pyramidal tetrahedral

trigonal pyramidal tetrahedral
Source: http://www.kshitij-iitjee.com
Consider the number of lone electron pairs and bonded pairs in each of the molecules below. The
repulsion between these lone electron pairs and bonded pairs determines the bond angles in each
molecule.
Water (H2O) has two bonded pairs of electrons and two lone pairs of
electrons. The order of repulsion is as follows:
lone pair - lone pair > lone pair - bond pair > bond pair - bond pair
The shape of water molecule is thus bent, with a bond angle of

104.5˚.

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Carbon dioxide (CO2) has a pair of double bonds. There are no lone
pairs of electrons. Therefore the pair of double bonds have equal
repulsion between them and are spaced at the maximum angle of
Carbon dioxide, CO2 180˚ to each other.
2 double bonds
Ammonia (NH3) has three bonded pairs of electrons and one lone
pair of electrons. The repulsion between the lone pair of electrons
and bonded pair is more than the repulsion between the boned
pairs. The shape of ammonia molecule is thus trigonal pyramidal,
with bond angles of 107 ˚.
Methane (CH4) has four bonded pairs of electrons. There are no lone
pairs of electrons. There is equal repulsion between all the four
bonded pairs. Thus all four bonds are at equally spaced around the
carbon atom at the maximum angle of 109.5˚.
Source: http://www.fccj.us/chm2045/StericNumber.htm
The melting point of 815 ˚C is characteristic of ionic compounds. Ionic compounds do not
conduct electricity in solid state. They conduct electricity either in molten state or when
dissolved in solution. In solution, ionic compounds dissociate into positive and negative ions in
polar solvents, which are responsible for conducting electricity. Ionic compounds are made up of
positive and negative ions in a three dimensional crystal lattice. A good example would be
sodium chloride (NaCl).
Covalent compounds, molecular compounds or molecules generally have low melting points and
do not conduct electricity either in solid state or even when dissolved in water. This is because

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there are no positive and negative ions present in molecules or they do not dissociate into
positive and negative ions when dissolved in water. An example could be methane (CH4).
Carbon dioxide is a non- polar molecule. Therefore solid carbon dioxide would have only van
der Waals forces between its molecules. The van der Waals forces or the weak intermolecular
forces of attraction can easily be overcome with a little amount of energy. That is the reason
solid carbon dioxide can be converted to gas (sublimed) at low temperature or without heating.
van der Waals forces is an example of induced dipole attraction, which arises when two non-
polar molecules are in close proximity of each other. Non-polar molecules that have induced
dipoles may induce neighboring non-polar molecules to have temporary dipole moments. A non-
polar molecule in close proximity of a non-polar molecule is able to distort the electron cloud of
the nonpolar species. The created distortion of the electron cloud causes the originally nonpolar
molecule or atom to acquire a dipole moment.
Carbon dioxide does not have hydrogen bonds, dipole-dipole attraction and ion-dipole attraction
between its molecules.
Hydrogen bonds occur in molecular compounds which have highly electronegative atoms (F, Cl,
O, N) attached to a hydrogen atom, such as water (H2O), hydrogen fluoride (HF), hydrogen
chloride (HCl), etc.
Example of hydrogen bonding between water molecules:

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Source: http://biogenesislab.blogspot.com
Dipole-dipole attraction occurs between molecular compounds which are polar or have net
dipole moments. Dipole-dipole forces are attractive forces between the positive end of one polar
molecule and the negative end of another polar molecule. Note that hydrogen bonding is a
special type of dipole-dipole attraction between molecules.
Example of dipole-dipole attraction between carbon monoxide molecules, HCl and I-Cl
molecules:
Dipole - induced dipole interactions occurs between polar and non-polar compounds. The polar
molecule in close proximity of a non-polar molecule is able to distort the electron cloud of the
neutral nonpolar species. The created distortion of the electron cloud causes the originally
nonpolar molecule or atom to acquire a dipole moment.
This induced dipole leads to attraction between the non-polar molecule and polar molecule.
Example of dipole - induced dipole interaction between water molecule (dipole) and oxygen
molecule (induced dipole).
Source: http://virtuallaboratory.colorado.edu

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Ion-dipole and ion-induced dipole forces are similar to dipole-dipole and induced-dipole
interactions but involve ions, instead of only polar and non-polar molecules.
Example of ion-dipole attraction between Na+ or Cl- (ion) and water molecules (dipole):
Source: http://www.ck12.org
Example of ion- induced dipole attraction between Fe2+ (ion) and O2 molecules (induced dipole):
Source: http://www.buzzle.com
In fact, PbH4 is less stable to heat than SiH4. Both PbH4 and SiH4 are simple molecular
compounds. Pb atom is bigger in size than Si atom. As such, the bond lengths in PbH4 is bigger
than the bond lengths in SiH4. Bigger bond lengths mean weaker bonds. Therefore it will be
easier to break the bonds in PbH4 than in SiH4 and hence PbH4 is less stable to heat than SiH4.
SnO is more basic than CO because SnO is a predominantly ionic compound and is an
amphoteric oxide.
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CO on the other hand is a polar covalent compound and reacts with water to form a solution of
carbonic acid.
Pb(IV) is relatively unstable as compared to Pb(II). As such Pb(IV) can readily reduce to Pb(II).
Pb4+ + 2e- → Pb2+
Pb has four valence electrons (5s25p2). However, the 5s2 electrons are tightly held by the nucleus
in Pb and are not easily removed. This is called the inert pair effect. As such Pb(II) is more stable
than Pb(IV).
Sn has four valence electrons (4s24p2). However, in Sn(II), only the 4p2 electrons have been
removed. As such, Sn(II) can be further and readily oxidised to Sn(IV). However, once Sn(IV)
forms, it would have obtained an stable electron configuration and any more electron removal
would not be as easy. Hence, Sn(IV) is not readily oxidised.
The melting point of elements increases because the strength of metallic bond increases from
sodium to aluminum. Nuclear charge increases in elements across the periodic table and as such
the strength of metallic bond increases. More energy will be required to break the metallic bonds
and hence melting point increases form left to right.
For example, aluminum has stronger metallic bonds in its metallic lattice as compared to sodium.
The reason for this is that the nuclear charge (number of protons) in aluminum is greater than
sodium, and as such there is a stronger attraction between aluminum atoms. More energy will be
required to break the metallic bonds in aluminum as compared to sodium and hence aluminum
has a higher melting point.
Note that the radius of the atoms will decrease across the periodic table because the increasing
nuclear charge in atoms holds on to the electrons more tightly. Similarly, metal ion radii will
decrease because there are fewer electrons, less shielding effect from electrons and more nuclear
attraction going from left to right.

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Comparison of sizes of atoms and their ions in picometers (pm).

Source: http://chemistry.stackexchange.com
Note that bonding remains metallic from sodium to aluminum because all are metals.
Group IV elements are C, Si, Ge, Sn and Pb. They form CO2, SiO2, GeO2, SnO2 and PbO2 as
dioxides.
CO2 is simple molecular compound and reacts with water to form carbonic acid. SiO2 is
macromolecular compound and does not react with water. GeO2, SnO2 and PbO2 are intermediate
between molecular and ionic and are amphoteric oxides. Therefore down the group, in general,
acidity of the dioxides decreases or the basicity of the dioxides increases.
Sodium hydride, NaH, is an ionic compound. Methane, CH4, and Silane, SiH4, are simple
molecular compounds.
Beryllium hydride, BeH2, (similar to MgH2) is a covalent compounds having polymeric
structures in which H atoms between beryllium atoms are held together by three centre – two
electron (3C - 2e) bonds or bridge bonds as shown below:

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If the beaker is cold to touch, it means that the reaction has absorbed energy from its
surroundings. As such it is endothermic. Since it also dissolved readily, its activation energy of
the reaction must be small as well.
This is an example of Markonikov’s addition, whereby the H from HCl adds to the carbon which
is already enriched with hydrogen and Cl gets added to the other carbon atom.
H3C H H3C H
C C + HCl Cl C C H
H3C CH2 CH3 H3C CH2 CH3
2-methylpent-2-ene 2-chloro-2-methylpentane
(major product)
The double bonded carbon on the left has two methyl groups attached to it. The double bonded
carbon on the right has a hydrogen and an ethyl group attached to it. Therefore the incoming H
will attach to the double bonded carbon on the right. Cl will attach to the double bonded carbon
on the left.

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When there is a single bond between two atoms, it is always a sigma (  ) bond. When there is a
double bond between two atoms, one is a sigma ( ) bond and one is a pi ( ) bond. When there is
a triple bond between two atoms, one is a sigma ( ) bond and two are pi ( ) bonds.
In this molecule, there are 10  bonds and 3  bonds, which are labeled below:
H 
 
C  C  C  C H

H   
H C H

H
The above reaction is between benzene (C6H6) and bromine (Br2). The reaction can be
represented using structural formulas as follows:

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H H
H H FeBr3 H Br
+ Br2 + HBr
H H H H
H H
benzene bromine bromobenzene hydrogen bromide

It can be seen that a hydrogen (H) in the benzene ring has been substituted by a bromine (Br).
As such this is a substitution reaction.
A compound exhibits optical isomerism if it has an asymmetrical carbon or in other words, four
different groups attached to it.
Choices A, B and D do not meet the above criteria. All compounds in A, B and D have a line of
symmetry.
C and D are automatically out because a molecule needs to have at least three carbon atoms to be
a ketone.
A is an ether. B is a ketone (propanone). C is an alkenol. D is an aldehyde (methanal).
O H H H
C C C C O
H3C CH2 O CH3 H3C CH3 H OH H

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Reaction D has the largest Ka, or acid dissociation constant (7.5 x 10-3). This means that it
undergoes the highest dissociation into products and has the highest concentration of products.
As a result it proceeds furthest towards right or towards completion.
OR
All the examples given above are examples of weak acids and they will dissociate partially in water.
HA(aq) + H2O(l) A-(aq) + H3O+(aq)

Weak acid Conjugate base
However, some of the acids will dissociate more than the others.
The acid dissociation constant (Ka) of a weak acid can be written as:
Ka = [A-] [H3O+]
[HA]
This implies that the more the dissociation of an acid, the higher the hydronium ion
concentration ([H3O+]) in its solution and as such, the larger the acid dissociation constant (Ka).
Of the four acids given above, the highest Ka is for phosphoric acid or H3PO4 (4.5 x 10-7).
Therefore, phosphoric acid is the strongest of all the four acids and undergoes the most dissociation.
PbCl2 → Pb2+ + 2Cl-

x 2x
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If the concentration of Pb2+ is x, then the concentration of 2Cl- will be 2x. This is because for
every 1 mole of PbCl2 that dissociates, 1 mole of Pb2+and 2 moles of Cl- is obtained.
As such the solubility product of PbCl2 would be:
Ksp = [Pb2+].[Cl-]2 =(x).(2x)2 = 4x3
For all the other salts (AgCl, AgNO3 and AgNO3), a working like the one above will show that
they have a solubility product expression of x2.
For example: PbNO3 → Pb2+ + NO3-

x x
Ksp = [Pb2+].[ NO3-] =(x).(x) = x2
Bronsted-Lowry acids are those that donate a proton. In the above example, CH3OH has donated
proton to NH2- in the forward reaction. In the same manner, in the backward reaction, NH3 has
donated a proton to CH3O-.
NH2- and CH3O- are examples of Bronsted-Lowry bases because they accept a proton in the
above forward and backward reactions, respectively.
Furthermore, to elaborate more relationships in the above reaction:

CH3OH is an acid and CH3O- is its conjugate base. NH2- is a base and NH3 is its conjugate acid.

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Summary table for galvanic and electrolytic cell characteristics:
Source: http://chemistryh2t13.blogspot.com/2011/02/electrolytic-cell-vs-galvanic-cell.html
See the example below for the difference between galvanic and electrolytic cell reactions using
copper and silver electrodes:
Note that the standard reduction potentials of the Cu2+/Cu and Ag+/Ag redox couples are as
follows: Cu2+(aq) → Cu(s) + 2e- E˚ = +0.34 V
Ag+(aq) → Ag(s) + e- E˚ = +0.80 V
Source: http://mcat-review.org/electrochemistry.php
Galvanic Cell Electrolytic Cell

Spontaneous reaction Non – spontaneous reaction
A voltmeter is used to measure the cell A source of electrical energy is needed to drive
potential (emf). a non-spontaneous redox reaction.
Converts chemical energy into electrical Converts electrical energy into chemical
energy. energy.
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Copper oxidises, is the anode and negative Copper reduces, is the cathode and negative
electrode: Cu(s) + 2e- → Cu2+(aq) electrode: Cu2+(aq) → Cu(s) + 2e-
Silver reduces, is the cathode and positive Silver oxidises, is the anode and positive
electrode: Ag+(aq) → Ag(s) + e- electrode: Ag(s) + e- → Ag+(aq)
Electrons travel from anode (-) to cathode (+) Electrons travel from anode (+) to cathode (-)
Salt bridge: Negative ions (Cl-) migrate Salt bridge: Negative ions (Cl-) migrate
towards anode (-); Positive ions (K+) migrate towards anode (+); Positive ions (K+) migrate
towards cathode (+). towards cathode (-).
In a cell notation, the half-cell reaction on the left depicts oxidation and the half-cell reaction on
the right depicts reduction. Therefore in the above case Ni metal is oxidised to Ni2+ ions, while
Cu2+ ions are being reduced to Cu metal.
Half-equations are as follows:

Oxidation: Ni(s) → Ni2+(aq) + 2e-
Reduction: 2e- + Cu2+(aq) → Cu(s)
SECTION B

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(Answer is rounded off to 2 decimal places).
1. Start with calculating the total number of valence electrons in H2SO4:
1 x S = 1 x 6 e- = 6 e-
4 x O = 4 x 6 e- = 24 e-
2 x H = 2 x 1 e- = 2 e-
Total = 32 valence electrons or 16 electron pairs
2. Place the S atom in the center and O and H atoms around it.
o
H o s o H
o
3. Place a pair of electrons between all the atoms to at least form a bond.
o
H o s o H
o
4. Since 12 electrons have been used up, 20 electrons are left. Place these as lone pairs around
atoms which need an octect. In other words, all the four oxygen atoms still need more electrons
to obtain an octect.

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o
H o s o H
o
5. After all the 32 valence electrons have been used up, it is evident that all the atoms have an
octect.
Therefore we have arrived to the Lewis structure of H2SO4. This answer is acceptable at this
level.
Note: The above Lewis structure is not the most stable one for H2SO4. The S atom can
accommodate more than eight electrons because it has empty d orbitals. The following Lewis
structure is the most stable one. However, because the concept of formal charges and
resonance structures are beyond the scope of study, it will not be covered here. This is just for
your information only.
o
H o s o H
o
Equation to be used: PV = nRT or since n = m/M, the formula PV = mRT/M can be used.
Mass (m) = 7.40 g
M (CO2) = 44 g mol-1
Standard Temperature = 0 ˚C = 273 K
Standard Pressure = 1 atm or 101.3 kPa
R = 8.314 J K-1 mol-1
Conversion factor: 1 L atm = 101.3 J
V=?

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( ) ( )( ).
= 3.77 L (rounded off to two decimal places)
This question deals with the relationship between the partial pressure of a gas, the total pressure
of the system and the mole fraction of the gas. It uses the principle that the partial pressure of an
individual gas is equal to the total pressure multiplied by the mole fraction of that gas.
(See Daltons’ Law of Partial Pressures as well).
Solution:
Methane = 0.31 mol

Ethane = 0.25 mol
Propane = 0.29 mol
Partial pressure of ethane (C2H6) =
( )
The standard heat of ionisation, or the standard enthalpy of ionisation, of an atom is the
minimum energy required to remove completely one mole of electrons from one mole of gaseous
atoms, measured under standard conditions.
The following equation shows an example of the standard heat of ionisation of the calcium atom:
Ca(g) → Ca+(g) + e-
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To be specific, the above equation is the standard heat of first ionisation or the first ionisation
energy of the calcium atom.
The first ionisation energy of is the minimum energy required to remove completely one mole of
the outermost electrons from one mole of gaseous atoms.
For aluminium (Atomic Number = 13), the electronic configuration is 1s22s22p63s23p1.

It has a partially filled outermost or the 3p subshell.
1s 2s 2p 3s 3p
For magnesium (Atomic number = 12), the electronic configuration is 1s22s22p63s2.

It has a fully filled outermost or the 3s subshell.
1s 2s 2p 3s
The electron to be removed from aluminium comes from a partially filled 3p subshell which is
less stable as compared to the fully filled 3s subshell of the magnesium atom. Therefore, it
requires relatively lesser energy to remove the 3p electron from aluminium than the 3s electron
in magnesium.
Source: http://ftp.stmarys-ca.edu/jsigman/Chem130/assignments/atomic-structure/quantum-numbers.htm

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The outermost electrons in Y are the two electrons in the 3s subshell (3s2).
1s 2s 2p 3s
For the 3s electrons, the principal quantum number (n) = 3, angular momentum quantum number
(l) = 0, magnetic quantum number (ml) = 0 and spin quantum number (ms) = + or .
Therefore, the quantum numbers for the two electrons are 3, 0, 0, + and 3, 0, 0, .
Note the order in which orbitals are filled with respect to their energies.
Source: http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch6/quantum.php
The atomic number for cobalt is 27. The electronic configuration for Co atom is
1s22s22p63s23p64s23d7.
The Co atom loses three electrons to form the Co3+ ion.

The three electrons will be lost from the 4s and 3d subshells. Both electrons from the 4s subshell
will be lost, while one electron will be lost from the 3d subshell.
As such, the electronic configuration of Co3+ ion will be 1s22s22p63s23p63d6.
Note that when filling of electrons take place in transition metals, the 4s subshell is filled first
because it is lower in energy than the 3d subshell. However, when electrons are lost from
transition metals, the 4s electrons are lost first because the 3d subshell is closer to the nucleus
and repels the 4s electrons, enabling it to be removed first.
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Carbon has a better ability to catenate than silicon, which means that carbon can form stable
compounds of long chain and rings of carbon atoms. Carbon can catenate to form compounds
with .
Silicon has one more shell than carbon and as such Si-Si bonds are longer and less stable than C-
C bonds, or C-C bond is stronger than Si-Si bond, or C-C bond energy is higher than Si-Si bond
energy, or C –C bond length is smaller than Si-Si bond length.
The C-C bond is as almost strong as the C-O bond and this makes the oxidation of the C-C bond
less favourable. Silicon does not undergo catenation because the strength of the Si-Si bond is less
than that of the Si-O bond (which is very favorable to form), meaning Si would rather form
oxides than catenate.
The standard enthalpy of formation is defined as the change in enthalpy when one mole of a
substance in the standard state (1 atm of pressure and 298 K) is formed from its pure elements
under the same conditions. It is usually denoted by ΔHf˚.
Therefore the equation for standard heat of formation of NO should have its elements (N2 and
O2) as reactants and 1 mole of NO as the product. At standard states (1 atm of pressure and 298
K), the reactants and products will all be in gaseous states.
N2(g) + O2(g) → NO(g)
The equation needs to be balanced because according to the definition only 1 mole of NO is
required:
N2(g) + O2(g) → NO(g)

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Note that it is not possible to calculate the standard heat of formation (ΔHf) of nitrogen
monoxide (NO) from the above two equations because their ∆H are not provided at standard
conditions.
However, the heat of formation (ΔHf) of nitrogen monoxide (NO) can be calculated as follows:
Given the two equations,
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l) ∆H = – 1170 kJ
4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(l) ∆H = – 1530 kJ
rearrange them so that they can be added to obtain the equation for heat of formation of nitrogen
monoxide (NO), which is:
N2(g) + O2(g) → NO(g)
Method 1:
Divide the first equation by 4:
( 4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O(l) ∆H = – 1170 kJ ) /4
Reverse the second equation and divide it by 4:
( 2N2(g) + 6H2O(l) → 4NH3(g) + 3O2(g) ∆H = + 1530 kJ ) /4
(Note that ∆H becomes positive when the equation is reversed)
The equations are now as follows:
NH3(g) + O2(g) → NO(g) + H2O(l) ∆H = –292.5 kJ
N2(g) + H2O(l) → NH3(g) + O2(g) ∆H = +382.5 kJ
Upon adding the two equations and canceling out the species occuring on both sides of the
equation, the following equation and ∆H are obtained, which is what we want:
N2(g) + O2(g) → NO(g) ∆H = +90 kJ

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The ∆H of +90 kJ is same as the heat of formation (ΔHf) of NO.

Therefore ΔHf of NO is +90 kJ.
This means that 90 kJ of energy is released when gaseous nitrogen monoxide, NO(g), is produced
from its elements, nitrogen and oxygen, in their gaseous states, i.e., N2(g) and O2(g).
Method 2:
The first equation remains same, reverse the second equation, add the two equations and then
divide it by 4.
The answer should be same as above, i.e.:
N2(g) + O2(g) → NO(g) ∆H = + 90 kJ
It is a reaction between a ketone and hydroxylamine. Note that aldehydes and ketones react with
hydroxylamine to produce oxime and water.
In this example, the nucleophilic nitrogen in the hydroxylamine will attack the carbonyl carbon
in the ketone. The products will be an oxime and water.
OH
O N
C + H2N OH C + H2O
H3C CH3 H3C CH3
propan-2-one hydroxylamine propanone oxime water
Note that amines react with acid chlorides to produce amides. In this example, the nucleophilic
nitrogen in the ammonia will attack the carbonyl carbon in the acid chloride. The products will
be an amide and water.

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O O
C + NH3 C + HCl
H3C Cl H3C NH2
ethyl chloride ammonia ethanamide hydrogen chloride
Note that aldehydes and primary alcohols can be oxidised by strong oxidising agents, such as
acidified potassium dichromate (H+/K2Cr2O7) or acidified potassium permanganate (H+/KMnO4)
to produce carboxylic acids.
In this example, ethanal will be oxidised by acidified dichromate solution to ethanoic acid.
O 2- + O
Cr 2O 7 /H
H3C C H3C C
H OH
ethanal (acidified dichromate) ethanoic acid
It is a secondary alcohol.
The reason is that the hydroxyl group (OH) is attached to a carbon atom that is attached to two other
carbon atoms or alkyl groups. Or the hydroxyl group (OH) is bonded to a secondary carbon.
This reaction is known as the dehydration of an alcohol to give an alkene. It is a type of

elimination reaction and sulphuric acid acts as a catalyst in this reaction. Water (H2O) is
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eliminated from the alcohol to give an alkene. However, due to the nature of the alcohol (2o or
secondary), two different alkenes can result as products, as shown below.
H OH H H H H H H
1 2 3 4 conc. H2SO4
H C C C C H H C C C C H
H H CH3 H
+ H C C C C H
H H CH3 H H H CH3 H
3-methylbutan-2-ol 2-methylbut-2-ene 3-methylbut-1-ene
The OH group is on C2. Note that there are hydrogens (H) on C1 and C3.
If the H and OH are lost as H2O from C2 and C3, respectively, then 2-methylbut-2-ene will be
the product. However, if the H and OH are lost as H2O from C1 and C2, respectively, then 3-
methylbut-1-ene will be the product.
In fact, a mixture of both products will form. For information purposes, it is worthy to note that
2-methylbut-2-ene will be the major product because it is a more substituted alkene and hence it
is more stable.
Also note that 2-methylbut-2-ene and 3-methylbut-1-ene are structural isomers of each other.
The overall charge on MoO2Cl2 is zero. MoO2Cl2 is molybdenum dioxydichloride.

The oxidation number of O is -2 and the oxidation number of Cl is -1 in such type of compounds.
Therefore the oxidation number of Mo in MoO2Cl2
Mo + 2(O) + 2(Cl) = 0
Mo + 2(-2) + 2(-1) = 0
Mo – 4 – 2 = 0
Mo = +6

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(i) Ethanal, C2H4O, (an aldehyde) can be obtained by oxidising ethanol, C2H5OH (an alcohol)
using a suitable oxidising agent. If a strong oxidising agent, such as acidified dichromate or
acidified permanganate is used, then controlled oxidation is required so that the ethanol only
oxidises to ethanal. If it is not controlled, then ethanal can further oxidise to ethanoic acid.
Alternatively, a milder oxidising agent, such CrO3 with pyridine, can be used to oxidise ethanol
to ethanal.
H + 2-
H /Cr2O 7 O
H3C C OH H3C C
controlled oxidation H
H
ethanol ethanal
H + -
O
H /MnO4
H3C C OH H3C C
controlled oxidation H
H
ethanol ethanal
H O
CrO 3/pyridine
H3C C OH H3C C
H H
ethanol ethanal
(ii) Chloroethane, C2H5Cl, (a haloalkane) can be obtained by reacting ethanol, C2H5OH (an
alcohol) with hydrogen chloride in presence of a catalyst or PCl5.
There are other methods as well, but it is beyond the scope of prescription.

28
Note that the square brackets ([ ]) around a substance indicate its concentration in an equilibrium
expression. The equilibrium expression (Kc) contains the product concentrations in the numerator
and the reactant concentrations in the denominator.
The number of moles of the substance in the reaction equation is indicated as the power to which
the concentration of the substance is raised to.
So the equilibrium expression (Kc) for the above system will have 1 mole of N2O and 1 mole of
NO2 as reactants in the gaseous states, while 3 moles of N2O will be the product in gaseous state.
Two half arrows in either direction between the reactants and products indicates that the system
is under equilibrium.
Sodium ethanoate (CH3COONa) dissociates in aqueous solution to form ethanoate ion and
sodium ion:
- +
CH 3COONa CH 3COO + Na
The ethanoate ion further accepts a proton form a water molecule to form CH3COOH and OH-
ions.
- -
CH3COO + H2O CH3COOH + OH
The presence of OH- ions makes the solution basic.
Deduce the oxidation and reduction half-equations from the ionic equation above.
The oxidation half-equation is: As2O3 → AsO43-
It can be shown that the oxidation state of As is +3 in As2O3, which increases to +5 in AsO43-.
As2O3 → AsO43-
2As + 3(O) = 0 As + 4(O) = -3

2As + 3(-2) = 0 As + 4(-2) = -3
2As - 6 = 0 As - 8 = -3
2As = 6 As = -3 + 8
29
As = +3 As = +5
Therefore, balance the oxidation half-equation:
As2O3 → AsO43-
Balance the number of As on both sides by having 2 moles of AsO43-:
As2O3 → 2AsO43-
There are 2 As on both sides now.
Balance the number of oxygens (O) on both sides by adding 5 water molecules (H2O) on the left
hand side.
5H2O + As2O3 → 2AsO43-
There are 8 O on both sides now.
Balance the number of hydrogens (H) on both sides by adding 10 protons (H+) on the right hand
side (i.e. balancing in acidic medium).
5H2O + As2O3 → 2AsO43- + 10H+
There are 10 H on both sides now.
On the left, the total charge is now 0, but on the right, the total charge is +4.
Balance the charges on both sides by adding 4 electrons on the right hand side.
5H2O + As2O3 → 2AsO43- + 10H+ + 4e-
There is a total charge of zero on both sides now.
The oxidation half-equation has been balanced.
It can be shown that the oxidation state of Mn is +7 in MnO4-, which decreases to +2 in Mn2+.
MnO4- → Mn2+
Mn + 4(O) = -1
Mn + 4 (-2) = -1
Mn -8 = -1
Mn = +7 Mn = +2
So the following reduction half-equation has to be balanced:

30
MnO4- → Mn2+
Mn atoms are balanced as it is.
Balance the number of oxygens (O) on both sides by adding 4 water molecules (H2O) on the
right hand side.
MnO4- → Mn2+ + 4H2O
There are 4 O on both sides now.
Balance the number of hydrogens (H) on both sides by adding 8 protons (H+) on the left side (i.e.
balancing in acidic medium).
8H+ + MnO4- → Mn2+ + 4H2O
There are 8 H on both sides now.
On the left, the total charge is now +7, but on the right, the total charge is +2.
Balance the charges on both sides by adding 5 electrons on the left hand side.
5e- + 8H+ + MnO4- → Mn2+ + 4H2O
There is a total charge of +2 on both sides.

The reduction half-equation has been balanced.
This can be done by adding together the balanced oxidation and reduction half-equations.
However, before we do that, we have to ensure that we end up with the same number of electrons
on both sides of the net-ionic equation. This is needs to be done to cancel out the electrons so
that we do not have any electrons remaining in the final equation.
In order to do this, we have to multiply both the half equations with values which will end up
giving the same number of electrons for both the half-equations.
5H2O + As2O3 → 2AsO43- + 10H+ + 4e-
5e- + 8H+ + MnO4- → Mn2+ + 4H2O
Since we have 4e- and 5e-, the common multiple for 4 and 5 would be 20.
Therefore multiplying the first equation by 5 and the second equation by 4 will result in 20e- in
both half-equations as follows:
( 5H2O + As2O3 → 2AsO43- + 10H+ + 4e- ) x 5

31
( 5e- + 8H+ + MnO4- → Mn2+ + 4H2O ) x 4
After multiplication:
25H2O + 5As2O3 → 10AsO43- + 50H+ + 20e-
20e- + 32H+ + 4MnO4- → 4Mn2+ + 16H2O
Adding the above two equations will give:
25H2O + 5As2O3 + 20e- + 32H+ + 4MnO4- → 10AsO43- + 50H+ + 20e- + 4Mn2+ + 16H2O
Canceling out the e-, H+ and H2O will result in the final balanced equation in acidic medium:
9H2O + 5As2O3 + 4MnO4- → 10AsO43- + 18H+ + 4Mn2+
Including the physical states of the reactants and products, the equation will be as follows:
9H2O(l) + 5As2O3(aq) + 4MnO4- (aq) → 10AsO43-(aq) + 18H+(aq) + 4Mn2+(aq)
The equation has been balanced in acidic medium.

32
SECTION C
The atomic number of hydrogen is 1 and its electronic configuration is 1s1. Since the s subshell
can accommodate a maximum of two electrons, the hydrogen atom can accept another electron
to obtain a full and stable electron shell configuration. It can do so through sharing of electrons
in a covalent bond and the H2 molecule is one such possibility.
H + H H H
The atomic number of helium is 2 and its electronic configuration is 1s2. Since the s subshell can
only accommodate a maximum of two electrons, the helium atom electron already has a full and
stable electron shell configuration. It cannot accept another electron through sharing of electrons
in a covalent bond and hence the He2 molecule is not a possibility.
The shape of the SO2 molecule is bent as shown below:
S
O O
Both the sulphur-oxygen bonds are polar, the polarities do not cancel out, and as such the SO2
molecule has a net dipole moment or is polar.
The shape of the CO2 molecule is linear as shown below:
O C O
Both the carbon-oxygen bonds are polar, however the polarities are in opposite directions and as
such cancel out. As such the CO2 molecule has a zero net dipole moment or is non-polar.

33
Comparison of the Lewis structures of CH4 and ∙CH3 are shown below:
H H
H C H H C
H H
CH4 is relatively unreactive because it has all the electrons as bonded pairs around atoms with
full and stable electron shells. On the other hand, ∙CH3 has a lone electron or unbonded electron
which is unstable and needs to pair up for stability, and this makes ∙CH3 a highly reactive
species.
Hund's rule states that every orbital in a subshell is singly occupied before any orbital is doubly
occupied. All of the electrons in singly occupied orbitals have the same spin (to maximize total
spin).
For example, carbon has when electrons are being filled in orbitals of carbon, then the first
electron is filled in the 1s subshell, which has one orbital. The second electron then pairs up with
the first electron in the 1s orbital because lower energy orbitals need to be fully filled before
electrons are added to next orbital with higher energy. The next higher energy subshell is 2s,
which has one orbital. The third electron gets filled in the 2s orbital, and the fourth one pairs up
with the third electron in the 2s orbital. The fifth electron gets filled in one of the three 2p
orbitals, where all three orbitals are of the same energy. The sixth and final electron cannot be
paired up with the fifth electron.
This filling is illustrated below, with highlights of the rules used:
The first electron is filled in the 1s orbital:
1s 2s 2p

34
The second electron is paired up with the first electron in the 1s orbital (Hunds rule applies here).
The spins of both electrons must be opposite to each other (Pauli Exclusion Principle applies
here - no two electrons in an atom can have identical quantum numbers):
1s 2s 2p
Moving on the next higher energy orbital, the third electron is filled in the 2s orbital:
1s 2s 2p
The fourth electron is paired up with the third electron in the 2s orbital (Hunds rule applies here).
The spins of both electrons must be opposite to each other (Pauli Exclusion Principle applies
here - no two electrons in an atom can have identical quantum numbers):
1s 2s 2p
Moving on the next higher energy orbital, the fifth electron is filled in the one of the orbitals of
the 2p subshell:
1s 2s 2p
The sixth electron is NOT paired up with the fifth electron in the 2s orbital. Instead, it is filled in
the next orbital of the 2p subshell. The spin of the two electrons should be same (Hunds rule
applies here).
1s 2s 2p
Molarity is concentration of a solution as moles of a solute per volume of solution.

Sucrose is the solute in this question.
Using the formula:
Molarity = Moles of sucrose = Mass of sucrose/ molar mass of sucrose

Volume of solution Volume of solution
= 100 g/342.3 g mol-1

1.50 L

35
= 0.19 M (Answer is rounded off to 2 decimal places)
To find the mass of calcium carbonate (CaCO3), the moles of CaCO3 needs to be determined.
To find the moles of CaCO3, the moles or mass of CO2 needs to be determined first.
To find the moles or mass of CO2 produced in the experiment, the ideal gas equation, PV= nRT,
or PV = mRT/M, respectively, can be used.
Using PV= nRT;
Pressure of CO2 = P – SVP of water = 400 kPa – 3.3 kPa = 396.7 kPa
Volume of CO2 = V = 250 mL = 0.250 L
R = 8.314 J K-1 mol-1
T = 27 ˚C = 300 K
Moles of CO2 = n = ?
n = PV/RT
= (396.7 kPa) (0.250 L) / (8.314 J K-1 mol-1) (300 K)
n = 0.398 mol
To find the moles of CaCO3, the mole ratio can be used from the equation:
CaCO3 : CO2
1 :1
x : 0.398 mol
(1) (x) = (1) (0.398 mol)

x = 0.398 mol
Therefore the moles of CaCO3 is 0.398 mol. (Molar mass of CaCO3 = 100 g mol-1).
Mass of CaCO3 = n x M
= 0.398 mol x 100 g mol-1
= 3.98 g (Answer rounded off to 2 decimal places).

36
Note: It is advisable that you do not round off values in your calculations until you arrive to the
final answer. This is to avoid carrying over errors to the final answer.
OR
Using PV= mRT/M;
Pressure of CO2 = P – SVP of water = 400 kPa – 3.3 kPa = 396.7 kPa
Volume of CO2 = V = 250 mL = 0.250 L
Molar mass of CO2 = M = 44 g mol-1
R = 8.314 J K-1 mol-1
T = 27 ˚C = 300 K
Mass of CO2 = m = ?
m = PVM/RT
= (396.7 kPa) (0.250 L) (44 g mol-1) / (8.314 J K-1 mol-1) (300 K)
m = 1.75 g
Moles of CO2 = m/M = 1.75 g / 44 g mol-1 = 0.0398 mol.
To find the moles of CaCO3, the mole ratio can be used from the equation:
CaCO3 : CO2
1 :1
x : 0.398 mol
(1) (x) = (1) (0.398 mol)

x = 0.398 mol
Therefore the moles of CaCO3 is 0.398 mol. (Molar mass of CaCO3 = 100 g mol-1).
Mass of CaCO3 = n x M = 0.398 mol x 100 g mol-1 = 3.98 g.
The Kinetic Molecular Theory of Gases states five postulates that describe the behavior of
molecules in a gas. An ideal gas exactly obeys the following five postulates of the Kinetic
Theory of Gases.
1. The molecules in a gas occupy negligible volume.
2. Gas molecules are in constant random motion.
3. The kinetic energy of all the gas molecules is proportional to the absolute temperature of the
gas.
37
4. All collisions between gas molecules and between molecules and walls of the container are
perfectly elastic (i.e. no energy is gained or lost during collisions).
5. Attractive or repulsive forces between gas molecules or between molecules and walls of the
container are negligible.
A real gas does not obey the ideal gas law or the five postulates of the Kinetic Theory of Gases.
At high pressures the gas no longer behaves as an ideal gas. At high pressures, the space between
the gas molecules becomes small and the volume is no longer negligible. This disobeys the first
postulate of the Kinetic Theory of Gases given above.
Also, at low temperatures, gas particles move slower and the attractive or repulsive forces
between the molecules are no longer negligible as well. This disobeys the fifth postulate of the
Kinetic Theory of Gases given above.
Therefore, at high pressures and low temperatures, the ideal gas will resemble a real gas.
(i) Transition metals have electrons in d orbitals. Copper is a transition metal and its electronic
configuration is 1s22s22p63s23p64s13d10.
The Cu metal 3d subshell have five d orbitals, and all the five d-orbitals have the same energy in
a free Cu atom or ion.
However when copper forms a compound, such as a metal complex, its ligands cause splitting of
the five d - orbitals into different energy levels. As a result, the d electrons of the Cu ion can now
absorb and transmit light of different wavelengths and hence appear coloured.
An example is copper sulphate solution, which has the light blue hexaaquocopper(II) ions,
[Cu(H2O)6]2+.
(ii) Transition-metal ions are able to form complex ions because they have empty valence-shell
orbitals that can accept pairs of electrons from a Lewis base. The Lewis bases are ligands which
contain at least one pair of nonbonding electrons that can be donated to a metal ion.
38
For example, water (H2O) can form a coordinate bond by donating its lone pair of electrons on
the oxygen atom to the empty valence-shell orbitals of the Cu2+ ion. Six H2O molecules can thus
coordinate to a Cu2+ ion and form a [Cu(H2O)6]2+ ion as shown below.
O
H H
Water molecule
[Cu(H2O)6]2+
Other examples are [Cu(NH3)4]2+ and [Cu(Cl)4]2-.
The solution will require heating. The formula used here would be ΔH = mcΔT , where:
ΔH = heat energy gained by the solution
c = the specific heat capacity of the solution (the heat energy needed to raise the temperature of 1
g of water by 1 °C) and has the value 4.18 J °C–1g–1.
m = the mass (in g) of solution being heated = 50 g.
∆T = the rise in temperature in °C.
Initial temperature = 25 ˚C
Final temperature = 90 ˚C
ΔT = Final temperature - Initial temperature = 90 ˚C - 25 ˚C = 65 ˚C
ΔH = mcΔT = 50 g x 4.18 J °C–1g–1 x 65 ˚C = 13585 J or 13.59 kJ
Therefore the amount of heat required is 13585 J or 13.59 kJ (2 decimal places).
(i) Energy is released when bonds are formed. Energy is needed to break the bonds.
The bond dissociation energy or the bond enthalpy is the amount of energy required to
break one mole of the bond to give separated atoms in the gaseous state.
39
HCl has one covalent bond between H and Cl atoms. The energy that will be required to
break the bonds of one mole of HCl molecules to give H and Cl in the gaseous state is the
H-Cl bond dissociation energy.
This can be represented in the equation form as follows:
HCl(g) → H(g) + Cl(g) ΔH will be positive.
The enthalpy change (ΔH) is indicated as positive because heat will be absorbed from the
surroundings by the reaction. The bond dissociation energy or the bond enthalpy is
always positive because the breaking of a bond requires an input of energy
(endothermic).
(ii) The enthalpy of combustion of a substance is the energy released when one mole of the
substance is completely burned in oxygen. The complete combustion of methane implies
that methane reacts or burns in oxygen to form carbon dioxide and water.
It can be represented as:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH will be negative.
Note that methane, oxygen and carbon dioxide are all in gaseous states, while water will
be in liquid state.
The enthalpy change (ΔH) is indicated as negative because heat will be released to the
surroundings by the reaction. The enthalpy of combustion is always negative because the
energy required to break bonds is always less than the energy released when bonds are
formed (exothermic).
It can be seen that Fe2+ is being reduced to Fe, while Zn is oxidised to Zn2+.
If the standard reduction potentials (E˚) of the two half-cells are compared, then it is obvious that
the standard reduction potential of the Fe2+/Fe couple is more positive (or larger) than the
standard reduction potential of the Zn2+/Zn couple.
i.e. -0.44 V > -0.76 V.
This implies that Fe2+ can be more easily reduced to Fe as compared to Zn2+ being reduced to
Zn. As such, Fe2+ will be reduced to Fe, while Zn will be oxidised to Zn2+, which confirms that
the above reaction will occur spontaneously.

40
OR
In other words, if the above reaction were to occur spontaneously as an electrochemical cell, then
the standard cell potential (E˚cell) should be positive.
Using the formula, find E˚cell:
E˚cell = E˚red - E˚oxd
Where:
E˚cell = Standard cell potential
E˚red = Standard reduction potential of the reducing half-cell (cathode)
E˚oxd = Standard reduction potential of the oxidising half-cell (anode)
For the above reaction, since Fe2+ is being reduced to Fe, while Zn is oxidised to Zn2+,
E˚cell = E˚red - E˚oxd

= E˚(Fe2+/Fe) - E˚(Zn2+/Zn)
= -0.44 V – (-0.76 V)
= +0.32 V
Since the E˚cell is positive, it confirms that the above reaction will occur spontaneously.
Compare the structures of the above two compounds:
OH H
H3C C CH3 H3C C O CH3
H H
2-propanol methoxyethane
2-propanol has a hydroxyl group (OH), where a hydrogen atom attached directly to an oxygen
atom. Any molecule which has a hydrogen atom attached directly to a highly electronegative
atom (O, N, F, Cl) is capable of hydrogen bonding. 2-propanol will form hydrogen bonds with
water molecules and therefore will be more soluble in water.
On the other hand methoxyethane (methylethyl ether) does not have an OH group and has
limited ability to form hydrogen bonds with water molecules. As a result it will be not as soluble
in water as 2-propanol.

41
Another similar example using ethanol and dimethyl ether is illustrated below. One molecule of
ethanol can form two hydrogen bonds with two water molecules, while one dimethyl ether
molecule can only form one hydrogen bond with a water molecule. As such, ethanol will be
more soluble in water than dimethyl ether.
Period II elements from left to right (refer to the Periodic Table) are:
Li, Be, B, C, N, O, F, Ne
Therefore the first four elements are Li, Be, B, C. The missing oxides in the table are that of Be
and C.
To form an oxide, beryllium (Be) will combine with oxygen (O). Be has 2 valence electrons
(1s22s2). O is 2 electrons short of a stable electron configuration (1s22s22p4). Therefore Be will
lose 2 electrons to O atom to form BeO. BeO is a giant ionic solid.
To form an oxide, carbon (C) will combine with oxygen (O). C has 4 valence electrons (2p2). O
is 2 electrons short of a stable electron configuration (1s22s22p4). C will form a pair of double
bonds with the two oxygen atoms. CO2 is a simple molecular compound and a gas at room
temperature.
The Lewis structure of CO2 is

42
O C O
C can also form a triple bond with the oxygen atom to form carbon monodioxide (CO).
CO is a simple molecular compound and a gas at room temperature.
The Lewis structure of CO is
From left to right Period II oxides are Li2O, BeO, B2O3, CO/CO2, NO/NO2/N2O/N2O4/N2O5, O2,
OF2.
Li2O is basic. It is and ionic compound and forms lithium hydroxide with water.
BeO is amphoteric. It can react with both acidic and basic solution.
In acids:
In bases:
B2O3 is acidic. It reacts with water to from boric acid.

CO is very weakly acidic. It reacts with the hydroxide ion.
CO2 is weakly acidic. It reacts with water to form very small amounts of carbonic acid.
NO and NO2 react with water to form nitric/nitrous acid.
O2 slightly dissolves in water to give a neutral solution.
OF2 reacts with water to form hydrofluoric acid.
Therefore the general trend is that Period II oxides character is that changes from basic to
amphoteric to acidic.
Boric acid (H3BO3) is formed as follows:
B2O3 + 3H2O → 2H3BO3

43
In a cell notation, the oxidation half-cell is on the left and the reduction half-cell is on the right.
Therefore, Sc is oxidising to Sc3+ and Zn2+ is reducing to Zn.
Balanced oxidation and reduction half-reactions are as follows:
Sc(s) → Sc3+(aq) + 3e-

Zn2+(aq) + 2e- → Zn(s)
Before the two half equation can be added, the number of electrons should be made same in both
the two half-equations, so that it can be cancelled in the net ionic equation. The common
multiple for 3 and 2 would be 6. Multiply the first equation by 2 and the second equation by 3.
( Sc(s) → Sc3+(aq) + 3e- ) x 2

( Zn2+(aq) + 2e- → Zn(s) ) x 3
We then get:
2Sc(s) → 2Sc3+(aq) + 6e-

3Zn2+(aq) + 6e- → 3Zn(s)
Now add the two half-equations to get the net ionic equation:
2Sc(s) + 3Zn2+(aq) + 6e- → 2Sc3+(aq) + 3Zn(s) + 6e-
Cancel out the 6e- electrons on both sides:
2Sc(s) + 3Zn2+(aq) → 2Sc3+(aq) + 3Zn(s)
Sc/Sc3+ is the oxidation half-cell and Zn2+/Zn is the reduction half-cell.

The standard cell potential, E˚cell and standard reduction potential of the reducing half-cell,
E˚(Zn2+/Zn) is given.
The standard reduction potential of the oxidising half-cell, E˚(Sc/Sc3+) can be found.
44
E˚cell = +1.32 V
E˚red = E˚(Zn2+/Zn) = -0.76 V
Using the formula, E˚cell = E˚red - E˚oxd, find E˚oxd:
Where:
E˚cell = Standard cell potential
E˚red = Standard reduction potential of the reducing half-cell (cathode or right hand side)
E˚oxd = Standard reduction potential of the oxidising half-cell (anode or left hand side)
E˚cell = E˚(Zn2+/Zn) - E˚(Sc/Sc3+)
+1.32 V = -0.76 V - E˚(Sc/Sc3+)
+1.32 V + E˚(Sc/Sc3+) = -0.76 V
E˚(Sc/Sc3+) = -0.76 V – (1.32 V)
E˚(Sc/Sc3+) = -2.08 V
The role of a buffer is to resist changes to the pH of a solution.

A buffer is an aqueous solution consisting of a mixture of a weak acid and its conjugate base, or
vice versa. An acidic buffer solution can be prepared using a weak acid and its conjugate base or
salt. A basic buffer solution can be prepared using a weak base and its conjugate acid or salt.
In this example, the buffer solution has been made from ammonia (NH3), which is a weak base
and ammonium ion (NH4+), which is its it conjugate acid (Or the buffer solution has been made
from ammonia (NH3), which is a weak base and ammonium chloride (NH4Cl), which is its salt).
Note that Cl- ions from NH4Cl are neutral and can be ignored as spectator ions. This is a basic
buffer solution and the buffer equilibrium is:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
When acid (HCl) is added in small amounts, the H3O+ reacts with NH3 to form NH4+ ions and
H2O as follows:
NH3(aq) + H3O+(aq) NH4+(aq) + H2O(l)
No new substance is formed since NH4+ is already a component of the buffer. Therefore, the pH
of the solution is maintained.
45
Similarly, if a base (OH-) was added in small amounts, the OH- reacts with NH4+ ions to form
NH3 and H2O as follows:
NH4+(aq) + OH-(aq) NH3(aq) + H2O(l)
Again, no new substance is formed since NH3 is already a component of the buffer. Therefore,
the pH of the solution is maintained.
(i) Triglycerides (a fat or oil) undergo alkaline hydrolysis with sodium hydroxide. The products
are glycerol and soap.
In this example, 1 mole of stearic acid will hydrolyse to give 1 mole of glycerol and 3 moles of
sodium stearate as follows:
O
H2C O C (CH2)16 CH3 H2C OH
O O
HC O C (CH2)16 CH3 NaOH HC OH +-
+ 3 Na O C (CH2)16 CH3
O
H2C O C (CH2)16 CH3 H2C OH
sodium stearate
stearic acid glycerol
This reaction is known as alkaline hydrolysis or saponification. The sodium stearate salt is found
in soap and this reaction is used by the soap manufacturing industry to make soap products.

46
(i) Chromium(III) ion is Cr3+.

It can be coordinated by six water molecules to form the following complex ion:
Cr3+ + 6H2O → [Cr(H2O)6]3+
(ii) Name of complex ion is hexaaquochromium(III) ion.
Where hexa means 6, aquo means water, chromium is the central metal atom, (III) is the
oxidation state of chromium, ion implies that the complex has an overall charge, which is +3.
Overall charge of the complex ion = oxidation state of metal – total charge on ligands
= oxidation state of chromium – (6 x charge on water)
= 3 – (6 x 0)
= +3
Note that H2O is a neutral molecule, hence it has an overall charge of zero.
If the standard reduction potentials (E˚) of the two half-cells are compared, then it is obvious that
the standard reduction potential of the NO3-/NO2- couple is more positive (or larger) than the
standard reduction potential of the I2/I- couple.
i.e. +0.94 V > +0.54 V.
This implies that NO3- can be more easily reduced to NO2- as compared to I2 being reduced to I-.
It also implies that NO3- can readily oxidise I- to I2, while it will reduce to NO2-.
Potassium iodide (KI) is a source of iodide (I-) ions in the above solution. Silver nitrate (AgNO3)
is the source of nitrate (NO3-) ions in the same solution.

47
I- is in now in the presence of NO3-. Therefore, NO3- will oxidise I- to I2, while it will reduce to
NO2-. This is the reason for the formation of iodine (I2) in the solution.
The half-reactions are as follows:
NO3- → NO2-
I- → I2
Balancing the half-reactions in acidic medium (note that acidified potassium iodide was used):
2e- + 2H+ + NO3- → NO2- + H2O

2I- → I2 + 2e-
Add the two half-reactions:
2e- + 2H+ + NO3- + 2I- → NO2- + H2O + I2 + 2e-
Cancel electrons on both sides to get the redox reaction:
2H+ + NO3- + 2I- → NO2- + H2O + I2
The Henderson-Hasselbalch equation can be used to solve this question.

For an acidic buffer solution, containing a weak acid (HA) and its conjugate base, the buffer
equilibrium is as follows:
HA(aq) + H2O(l) A-(aq) + H3O+(aq)

Weak acid Conjugate base
The Henderson-Hasselbalch equation derived from the acid dissociation constant (Ka) of the
above acid will be:
pH = pKa + log [A-]

[HA]
The example in the question is an acidic buffer solution, containing a weak acid (CH3COOH)
and its conjugate base (CH3COO-). Note that CH3COONa dissociates in water to give CH3COO-
and Na+. Na+ ions from CH3COONa are neutral and can be ignored as spectator ions. The buffer
equilibrium is as follows:
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

48
To calculate the mass of sodium ethanoate (CH3COONa), we need to first find the moles of
CH3COONa. This will be the same as the moles of CH3COO- ions, which can be found using the
Henderson-Hasselbalch equation:
pH = pKa + log [A-]
[HA]
4 = 4.76 + log [CH3COO-]

[CH3COOH]
-0.76 = log [CH3COO-]

0.10
0.1738 = [CH3COO-]
0.10
[CH3COO-] = 0.01738 mol/L
If 0.01738 moles of CH3COO- ions are present in 1 liter (1000 mL), then 0.001738 moles of
CH3COO- ions will be present in 100 mL.
CH3COONa CH3COO- + Na+
Moles of CH3COO- ions = Moles of CH3COONa
Mass of sodium ethanoate (CH3COONa) = n x M

= 0.001738 mol x 82.03 g mol-1
= 0.14 g (rounded off to 2 decimal places)
The dissociation equation for acetic acid is:
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

x x
Ka = [CH3COO-] [H3O+]
[CH3COOH]
1.8 x 10-5 = (x)(x)

0.25 M
x2 = (1.8 x 10-5) (0.25 M) = 4.5 x 10-6

49
x = 2.12 x 10-2 M or 2.12 x 10-2 mol L-1
Therefore [H3O+] = [H+] = 2.12 x 10-2 M or 2.12 x 10-2 mol L-1
Any aqueous solution will contain:
- The substances dissolved (either in molecular form or as ions)

- Liquid water, H2O(l)
- Hydronium and hydroxide ions, H3O+(aq) and OH-(aq)
Ammonium chloride (NH4Cl) is a strong electrolyte and will dissociate completely in water as
follows (0.1 mol is taken as an example to compare the amounts of different species present):
NH4Cl(s) → NH4+(aq) + Cl-(aq)

0.1 mol 0.1 mol 0.1 mol
The ammonium ion is the conjugate acid of a weak base and thus will be hydrolysed. A few
ammonium ions, NH4+(aq), will further react with water to form ammonia and hydronium ions as
follows:
NH4+(aq) + H2O(l) → NH3(aq) + H3O+(aq)

0.1 mol - x x x
This reaction creates an excess of hydronium ions making the solution acidic.
Dissociation of water:
The concentration of water in dilute solutions can be calculated as follows:
If 1 L of water = 1000 g of water, then
Moles of water = mass of water / molar mass of water = 1000 g / 18 g mol-1 = 55.55 mol.
Concentration of water = moles of water / volume of water = 55.55 mol / 1 L = 55.55 mol L-1.
Water ionises to a very small extent into hydronium and hydroxide ions:
2H2O(l) → H3O+(aq) + OH-(aq)
In neutral solutions (pH = 7), the concentrations of H3O+(aq) and OH-(aq) would be:

50
[H3O+] = [OH-] = 1 x 10-7 mol L-1
However, the ammonium chloride solution is acidic due to the increased H3O+ concentration as
shown in the equation above: NH4+(aq) + H2O(l) → NH3(aq) + H3O+(aq)
This implies that [H3O+] > [OH-] or [H3O+] > 1 x 10-7 mol L-1 and [OH-] < 1 x 10-7 mol L-1.
Therefore, the species present in the solution of NH4Cl will be H2O, NH4+, Cl-, NH3, H3O+ and
OH-. Listing the concentrations of each species from the analysis done above, in decreasing
order, we have:
[H2O] = 55.55 mol L-1
[Cl-] = 0.1 mol L-1
[NH4+] < 0.1 mol L-1 (Note that [NH4+] < [Cl-] because NH4+ undergoes further dissociation)
[NH4+] > [NH3] > 1 x 10-7 mol L-1
[H3O+] = [NH3] > 1 x 10-7 mol L-1
[OH-] < 1 x 10-7 mol L-1
When placed in order, the list of species with decreasing concentrations will be:
[H2O] > [Cl-] > [NH4+] > [NH3] = [H3O+] > [OH-]
When represented on the bar graph, the relative concentrations of all species would look like the
following (note that H2O and NH3 bars were already drawn):

51
Compound A, C2H4 or ethene (an alkene), which has converted to Compound B, C2H5OH, which
is ethanol (an alcohol).
This is a hydration reaction and Reagent X will be acidified water or water in the presence of an
acid or dilute sulphuric acid.

52
The hydration reaction is shown below:
H H + H H
H2O/H
C C H C C OH
or dilute H2SO4
H H H H
ethene ethanol
Compound A is C2H4 or ethene (an alkene), which has converted to Compound F, C2H5Br or
bromoethane or ethyl bromide (an alkyl halide or haloalkane). Therefore the type of reaction I is
an addition or hydrohalogenation reaction. The reagent will be hydrogen bromide (HBr).
The addition or hydrohalogenation reaction is shown below:
H H H H
C C + HBr H C C Br
H H H H
ethene hydrogen bromide bromoethane
Type of reaction II
Compound F, C2H5Br or bromoethane (an alkyl halide or haloalkane) has converted to

Compound A, C2H4 or ethene (an alkene). Therefore the type of reaction II is elimination /
dehydrohalogenation reaction. Hydrogen bromide (HBr) is eliminated from bromoethane to give
a double bond between the two carbon atoms. A molecule of HBr is eliminated, hence it is also
called dehydrohalogenation. The reagent will be alcoholic potassium hydroxide (KOH in
ethanol).
The elimination / dehydrohalogenation reaction is shown below:
H H H H
H C C Br alcoholic KOH C C + HBr
H H H H
bromoethane ethene hydrogen bromide

53
Compound B, C2H5OH or ethanol (an alcohol) is reacted with reagent acidified potassium
dichromate (K2Cr2O7/H+), which is a strong oxidising agent. This will result in the oxidation of
ethanol to Compound C, which is ethanoic acid or CH3COOH.
Therefore the type of reaction is oxidation.
The oxidation reaction is shown below:
H H H O
+
K2Cr 2O 7/H H C
H C C OH C
H H H OH
ethanol ethanoic acid

Compound F, C2H5Br or bromoethane (an alkyl halide or haloalkane) is reacted with ammonia,
NH3, which is a nucleophile.
Therefore, this will be a nucleophilic substitution reaction, where aminoethane or ethanamine or
ethylamine or C2H5NH2 (an amine) will form as Product G.
The nucleophilic substitution reaction is shown below:
H H H H
H C C Br + NH3 H C C NH2 + HBr
H H H H
Bromoethane ammonia hydrogen bromide
ethanamine
Compound G, C2H5NH2 or aminoethane (an amine) is reacted with CH3COCl or ethanoyl

chloride (an acyl chloride). C2H5NH2 is a nucleophile in this reaction.
Acid chlorides (acyl chloride) react with ammonia, 1° amines and 2° amines to form amides.
Therefore, this will be a nucleophilic addition / elimination reaction, where N-ethylethanamide

(an N-substituted amide) and ethylammonium chloride will form. The major product, Compound
H, would be N-ethylethanamide.

54
The reaction is shown below:

O H
O -
+
2 H3C CH2 NH2
+ H3C C H3C C + H3C CH2 N H Cl
Cl N CH2 CH3 H
H
ethanamine ethanoyl chloride
N-ethylethanamide ethylammonium chloride
Notice that, unlike the reactions between ethanoyl chloride and water or ethanol, hydrogen
chloride (HCl) is not produced. Any hydrogen chloride formed would immediately react with
excess ethylamine to give ethylammonium chloride.
Compound C is ethanoic acid or CH3COOH, which reacts with Compound B, ethanol or

C2H5OH, in presence of concentrated sulphuric acid (conc. H2SO4) to form ethyl ethanoate (an
ester) and water as follows:
H H H O H O
Conc. H2SO4
H C C OH + H C C H C C + H2O
H H H OH O CH2 CH3
H
ethanol ethanoic acid ethyl ethanoate water
Therefore Compound D would be ethyl ethanoate as the major product.
Compound A, C2H4 or ethene (an alkene), is reacted with acidified potassium permanganate
(KMnO4/H+), which is a strong oxidising agent. The product will be methanoic acid.
The reaction is as follows:
+
H H KMnO4/H O
C C 2 H C
H H OH
ethene methanoic acid

Therefore Compound E is methanoic acid.
55
The functional groups in propanone and methylethanamine are the carbonyl and amine groups,
respectively, as shown below.
O
C H3C CH2 N CH3
H3C CH3
H
carbonyl group amine group
propanone methylethanamine
THE END

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1

FIJI YEAR 13 CERTIFICATE EXAMINATION 2014

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

For n = 7, l = 0, 1, 2, 3, 4, 5, 6 (7s, 7p, 7d, 7f, 7g, 7h,)

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

trigonal pyramidal tetrahedral

The shape of water molecule is thus bent, with a bond angle of

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

Example of hydrogen bonding between water molecules:

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

Pb4+ + 2e- → Pb2+

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

Comparison of sizes of atoms and their ions in picometers (pm).

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

benzene bromine bromobenzene hydrogen bromide

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

HA(aq) + H2O(l) A-(aq) + H3O+(aq)

PbCl2 → Pb2+ + 2Cl-

As such the solubility product of PbCl2 would be:

Ksp = [Pb2+].[Cl-]2 =(x).(2x)2 = 4x3

For example: PbNO3 → Pb2+ + NO3-

Ksp = [Pb2+].[ NO3-] =(x).(x) = x2

Furthermore, to elaborate more relationships in the above reaction:

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

Summary table for galvanic and electrolytic cell characteristics:

Galvanic Cell Electrolytic Cell

Half-equations are as follows:

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

(Answer is rounded off to 2 decimal places).

1. Start with calculating the total number of valence electrons in H2SO4:

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

= 3.77 L (rounded off to two decimal places)

Methane = 0.31 mol

Partial pressure of ethane (C2H6) =

For aluminium (Atomic Number = 13), the electronic configuration is 1s22s22p63s23p1.

For magnesium (Atomic number = 12), the electronic configuration is 1s22s22p63s2.

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

The Co atom loses three electrons to form the Co3+ ion.

N2(g) + O2(g) → NO(g)

N2(g) + O2(g) → NO(g)

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

Given the two equations,

4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l) ∆H = – 1170 kJ

4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(l) ∆H = – 1530 kJ

N2(g) + O2(g) → NO(g)

Divide the first equation by 4:

( 4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O(l) ∆H = – 1170 kJ ) /4

Reverse the second equation and divide it by 4:

( 2N2(g) + 6H2O(l) → 4NH3(g) + 3O2(g) ∆H = + 1530 kJ ) /4

(Note that ∆H becomes positive when the equation is reversed)

The equations are now as follows:

NH3(g) + O2(g) → NO(g) + H2O(l) ∆H = –292.5 kJ

N2(g) + H2O(l) → NH3(g) + O2(g) ∆H = +382.5 kJ

N2(g) + O2(g) → NO(g) ∆H = +90 kJ

© MINISTRY OF EDUCATION, FY13CE 2014: CHEMISTRY.

The ∆H of +90 kJ is same as the heat of formation (ΔHf) of NO.

The answer should be same as above, i.e.:

N2(g) + O2(g) → NO(g) ∆H = + 90 kJ

propan-2-one hydroxylamine propanone oxime water