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MINISTRY OF EDUCATION

FIJI SEVENTH FORM CERTIFICATE EXAMINATION 2013

CHEMISTRY PAPER 1

QUESTIONS

AND

DETAILED SOLUTIONS

WITH

ADDITIONAL NOTES

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SECTION A

Answer: C

The atomic number of iron is 26. When filling the orbitals for any atom, an order is followed,
whereby the orbital of the lowest energy is filled first, then the next higher orbital and so on.

The order is as follows:

Source: http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch6/quantum.php

Also note that an s subshell has one orbital and can only accommodate a maximum of 2
electrons, a p orbital has three orbitals and can accommodate a maximum of 6 electrons and a d
subshell has five orbitals and can accommodate 10 electrons.

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Subshell No. of orbitals Box representation Maximum no. of


electrons

s 1 1

p 3 6

d 5 10

Therefore for an iron atom, the 26 electrons will be filled as follows:

1s22s22p63s23p64s23d6

If the same is shown in box representation of orbitals, then it will be:

1s 2s 2p 3s 3p 4s 3d

Answer: A

The atomic number of sodium is 11. It has 11 electrons and its electronic configuration is
1s22s22p63s1.

The valence electron of sodium is in the 3s subshell (3s1).

Therefore, the Principal Quantum Number, n, is 3 (third shell). The Angular Momentum
Quantum Number, l, is 0 (the s subshell). The Magnetic Quantum Number, ml, is 0 (the s
orbital). The spin quantum number, ms, is either + or - (clockwise or anti-clockwise spin).

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Therefore the set of quantum numbers describing the outermost electron in sodium would be
either n = 3, l = 0, ml = 0, ms = + or n = 3, l = 0, ml = 0, ms = - .

Answer: D

Group II elements are alkaline earth metals and have 2 valence electrons. Group VI elements
have 2 electrons short of a full and stable octet. As such, if a Group II element, X, combines with
a Group VI element, Y, then an ionic compound will result. X will lose 2 electrons to form the
X2+ ion, while Y will gain 2 electrons to form Y2- ion. The ionic compound will have the
formula XY. Examples will be MgO, BeO, CaO, etc.

XY, being an ionic compound, will readily dissolve in water. However, BeO is an example of a
compound of Groups II and VI that does not dissolve in water. That is why D will be the least
likely to be true.

Answer: B

The most polar bond is O-H, which has the highest electronegativity difference.

N-F 4.0-3.5 = 0.5

O-H 3.5-2.2 =1.3

N-O 3.5-3.5 = 0.5

N-H 3.0-2.2 = 0.8

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Answer: D

Let P1 = standard atmospheric pressure = 1 atm, V1 = 60 cm3, V2 = 20 cm3, P2 = ?

P1V1 = P2V2

V2 = P1V1 / P2 = (1 atm) (60 cm3) / (20 cm3) = 3 atm

Answer: D

Hydrogen bonds occur in molecular compounds which have highly electronegative atoms (F, Cl,
O, N) attached to a hydrogen atom, such as in ammonia (NH3), water (H2O), hydrogen fluoride
(HF), hydrogen chloride (HCl), etc. Oxygen, chlorine and fluorine are examples of highly
electronegative atoms.

Both, NH3 and H2O, will form hydrogen bonds in liquid state, as shown below.

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However, because the O-H bond is more polar than N-H bond (as shown in Question 4), H2O
will have more stronger hydrogen bonds in liquid state.

H2S will not form hydrogen bonds because the S-H bond is not that polar.

CH4 molecules will not form hydrogen bonds because it is a non-polar molecule.

Answer: C

Solutions of transition metal ions can be coloured. An example is copper sulphate solution, which
has the light blue hexaaquocopper(II) ions, [Cu(H2O)6]2+.
In Cu metal, the 3d subshell had 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.

Coordination number is the number of ligands that coordinate to a central atom or ion in metal
complex or metal complex ion. Transition metal complexes or transition metal ion complexes
can have different coordination numbers. For example, the coordination number of
hexaaquocopper(II) ion, [Cu(H2O)6]2+, is 6, while the coordination number of
tetraamminecopper(II) ion, [Cu(NH3)4]2+, is 4.

Transition elements can exhibit more than one oxidation state when they form compounds. The
similarity in ionization energies and the relatively small increase in successive ionization
energies lead to the formation of metal ions with the same charge for many of the transition
metals. Due to a small increase in successive ionization energies, most of the transition metals
have multiple oxidation states separated by a single electron.

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Comparison of successive molar ionisation energies (in kJ mol−1) for the first 10 electrons of
transition metals:

Source: https://en.wikipedia.org/wiki/Molar_ionization_energies_of_the_elements

Some examples common oxidation states of transition elements are given below:

Source: http://chemwiki.ucdavis.edu/

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Across the Periodic Table, the first ionisation energy of transition elements gradually increases,
though irregular (due to partially and fully filled 4s and 3d orbitals for some elements), because
of more tightly bound by the increasing nuclear charge. However, the difference is small
between the first ionisation energies of the transition elements.

There is a small difference between the first ionisation energies of iron and copper. Compare the
electronic configurations of Fe, 1s22s22p63s23p64s23d6 and Cu, 1s22s22p63s23p64s23d9. In both
cases, the first electron will be lost from the 4s subshell.

Answer: C

Group IV elements have the general valence electron configuration, ns2np2. For example,
carbon’s valence electron configuration is 2s22p2. This means that Group IV elements can have a
stable +4 oxidation state. In fact, carbon, silicon, germanium, tin and lead all are capable of
forming compounds with oxidation states of +2 by using only the np2 electrons only. This arises
due to the tightly held ns2 electrons by the nucleus, resulting in the phenomenon called inert pair
effect. Down the group, the +2 oxidation state (the lower oxidation sate) becomes more stable
due to enhanced inert pair effect from increasing nuclear charge.

The inert pair effect is more pronounced in Sn and Pb, who form more stable +2 oxidation states.
For example, 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).

Electronegativity of Group IV elements decreases down the group.

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Answer: A

The standard heat or 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 carbonic acid, H2CO3 should have its
elements (H2, C and O2) as reactants and 1 mole of H2CO3 as the product. For this example, at
standard states (1 atm of pressure and 298 K), the reactants and the product will be in their
standard states.
Therefore the only conditions that match these are in option A.
In option B, the equation has a compound (CO2) as a reactant. In option C, hydrogen (H) is not in
its elemental state. In option D, the reactants are compounds and not elements.

Answer: C

394 kJ of energy is released when 1 mole of carbon is burnt. How many moles of carbon will be
burnt to produce 1000 kJ of energy?

Use ratio method: Energy released : moles of C

394 kJ : 1 mol

1000 kJ :x

Cross multiply and solve for x. x = 2.538 mol = moles of C burnt. Ar of C = 12 g mol-1.

Mass of C = n x M = 2.538 x 12 g mol-1 = 30.5 g

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Answer: D

Geometrical isomers are those compounds which have the same molecular formula, same bonds
but different spatial arrangement. Geometrical isomerism are shown by compounds with carbon-
carbon double bonds where the molecules that are locked into their spatial positions with respect
to one another due to the double bond. The isomers can be cis and trans. Cis isomers will have
the same groups on both the carbon atoms on the same side of the double bond. Trans isomers
will have the same groups on both the carbon atoms on the opposite sides of the double bond.

The compounds in options A, B and C have double bonds and but would not be able to show
geometrical isomerism. A, B and C are:

H Br Br Br H Br
C C C C C C
H Br Br Br H H

1,1-dibromoethene tetrabromoethene bromoethene

Only option D is a compound, which has a double bond between carbon atoms and will show cis
and trans isomerism as follows:

H H Br H

C C C C

Br Br H Br

cis-1,2-dibromoethene trans-1,2-dibromoethene

Both Br groups are on Both Br groups are on


the same side of the the opposite sides of the
double bond. double bond.

Answer: C

2-chloropropane (CH3CHClCH3) is an alkyl halide. It has a chlorine atom, which is highly


electronegative, on the second carbon atom. The second carbon atom is thus slightly positive and
can be attacked by a negatively charged species. Hydroxide ion (OH-) is a strong nucleophile.
Therefore the hydroxide ion will attack the carbon bonded to chlorine atom and make the

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chlorine atom leave as a chloride ion. The product will be 2-propanol. Therefore this is a
nucleophilic substitution reaction. The reaction will be as follows:

H Cl H H OH H
-
H C C C H + OH H C C C H + Cl
-

H H H H H H
2-chloropropane hydroxide ion propan-2-ol chloride ion

An example of an addition reaction will be one where double bond is broken to add two groups,
such as when hydrogen bromide (HBr) reacts with ethene (C2H4) as shown below:

H H H H
C C + HBr H C C Br
H H H H

ethene hydrogen bromide bromoethane

An example of a condensation reaction will be one where water (H2O) is a product. An alcohol
will react with a carboxylic acid in presence of concentrated sulphuric acid to form an ester and
water, as shown below:

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

An example of an electrophilic substitution reaction will be benzene reacting with Br2 in


presence of FeBr3 as a catalyst, as shown below: A Br atom has substituted a H in the benzene
ring.

H H

H H FeBr3 H Br

+ Br2 + HBr

H H H H

H H

benzene bromine bromobenzene hydrogen bromide

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Answer: B

The basicity strength of amines depends on the number of alkyl (R) groups on the N atom. The
more the number of alkyl groups, the more basic an amine will be. The reason is that the alkyl
(R) groups make the amine more basic by electron donating inductive effect on to the nitrogen
atom. Similarly, the cation formed by a amine with the most alkyl (R) groups will be more
stable because the positive charge on the nitrogen will be stabilized by the electron donating
inductive effect of the alkyl (R) groups.

Therefore, generally, the increasing order of basicity of amines will be:

Therefore, the increasing order of basicity of the above compounds will be as follows:

NH3 < CH3CH2NH2 < (CH3)2NH < (CH3)3N

least basic most basic

OR (using structures)

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Answer: A

In option A, the oxidation of ethanal (an aldehyde) will result in the formation of ethanoic acid (a
carboxylic acid).

O O
oxidation
H3C C H3C C
H OH

ethanal ethanoic acid

In option B, fermentation of glucose will result in the formation of ethanol.

In option C, the reaction steam with ethene will result in the formation of ethanol as shown
below.

H H steam (H2O) H H
C C H C C OH
H H H H

ethene ethanol

In option D, the reaction of ethyl ethanoate with water will result in the formation of ethanol and
ethanoic acid as shown below (Hydrolysis of an ester gives an alcohol and a carboxylic acid).

H H H O
H O
+ H2O H C C OH + H C C
H C C
H H H OH
H O CH2 CH3
ethanol ethanoic acid
ethyl ethanoate water

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Answer: C

Alanine is an amino acid. Amino acids have two main functional groups, an amine and a
carboxyl functional group, as shown below.

H O

H N C C OH

H CH3

carboxyl group
amine group

Answer: D

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.

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The acid dissociation constant (Ka) of a weak acid can be written as:

Ka = [A-] [H3O+]
[HA]

This implies that the lesser the dissociation of an acid, the lower the hydronium ion concentration
([H3O+]) in its solution and as such, the smaller the acid dissociation constant (Ka). Of the four
acids given above, the smallest Ka is for carbonic acid (4.5 x 10-7). Therefore, carbonic acid is the
weakest of all the four acids.

OR

Similarly, the pKa of an acid is related to its Ka:


pKa = - log Ka

This mathematical relationship means that the, smaller the Ka of an acid, the larger is its pKa.
Carbonic acid has the largest pKa value of all the four acids (6.35). Therefore, carbonic acid is the
weakest of all the four acids.

Note that Ka values are very small and it is converted to pKa values, which are much easier to work
with.

Answer: A

A buffer is an aqueous solution consisting of a mixture of a weak acid and its conjugate base, or
weak base and its conjugate acid. The role of a buffer is to resist changes to the pH of a solution.
When small amounts of an acid or base is added to the aqueous solution, the buffer will counter its
effect by reestablishing equilibrium so that no new substance is formed.
Option B is incorrect because the resulting mixture will be more than 100 cm3.

Answer: B

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In S2O32-, the overall charge is -2 and the oxidation state of O is -2.


Therefore, 2S + 3(-2) = -2
2S – 6 = -2
2S = 4
S = +2

Answer: A
Options B-D are all correct. An electrochemical cell can be recharged. See the summary below
for an electrochemical cell.

Source: http://chemistryh2t13.blogspot.com/2011/02/electrolytic-cell-vs-galvanic-cell.html

Example of a galvanic cell:

Summary of the galvanic cell


Spontaneous reaction
A voltmeter is used to measure the cell potential (emf).
Converts chemical energy into electrical energy.
Copper oxidises, is the anode and negative electrode: Cu(s)
+ 2e- → Cu2+(aq)
Silver reduces, is the cathode and positive electrode: Ag +(aq)
→ Ag(s) + e-
Electrons travel from anode (-) to cathode (+)
Salt bridge:
Negative ions (Cl-) migrate towards anode (-);
Source: http://mcat- Positive ions (K+) migrate towards cathode (+).
review.org/electrochemistry.php

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SECTION B

Electronegativity is an atom’s ability to attract a shared pair of electron in a bond. The


knowledge of electronegativity trends in the periodic table is required in this question.

The electronegativity of elements increases across the period and decreases down the group in
the periodic table. Electrons are added to the same shell across the period and the nuclear charge
increases across the period. This increases the electronegativity of elements across the period.

Down the group, new shells are added. This increases the atomic radii and increase in the
shielding effect. The nuclear charge becomes less effective in attracting pair of electrons and
hence the electronegativity decreases down the group.

Looking at the positions of the four elements in the Periodic Table below, it is obvious that Cs is
down most in a group and hence will be the least electronegative element. Magnesium will be
less electronegative than nitrogen, because it is far left in the periodic table. Fluorine will be
more electronegative than nitrogen because it is far right in the periodic table.

As such the order of increasing electronegativity will be Cs < Mg < N < F.

In fact, Cs and Mg are highly electropositive elements.

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The atomic number of chlorine (Cl) is 17, which means it has 17 electrons in its three shells.
Chloride ion (Cl-) has 18 electrons in its three shells. The numbers of protons in both, Cl and Cl-,
are 17. This means that the nuclear charge in Cl is same as Cl-. However, the extra electron in Cl-
contributes to extra shielding effect, which causes the nucleus to be less effective in being able to
hold on to its electrons as tightly as it does in Cl. Therefore the electrons of Cl- will be further
from the the nucleus and as such the radius of Cl- ion will be greater.

HCl is an asymmetrical molecule and has two atoms of large electronegativity difference bonded
together. Cl is a highly electronegative element, while H is of lower electronegativity. This
enables the bonded electron pair or electron cloud to be permanently distorted toward Cl atom.
This creates a permanent dipole moment in HCl, whereby the Cl atom carries a partial negative
charge, while the hydrogen atom carries a partial positive charge. +ᵟH-Clᵟ-

The mole fraction of glucose can be calculated as follows:

Find the moles of glucose (solute):

(Mass of glucose = 25 g; Molar mass of glucose = 180 g mol-1)

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n = m/Mr = 25 g / 180 g mol-1 = 0.139 mol

Find the moles of water (solvent):

(Mass of water = 250 g; Molar mass of water = 18 g mol-1)

n = m/Mr = 250 g / 18 g mol-1 = 13.889 mol

Find total moles of glucose (solute) and water (solvent):

0.139 mol + 13.889 mol = 14.028 mol

Therefore,

Mole fraction of glucose = moles of glucose / (moles of glucose + moles of water)

= 0.139 / 14.028 = 9.91 x 10-3

Molality = moles of solute / kg of solvent


= moles of glucose / kg of water
= 0.139 mol / 0.250 kg
= 0.56 mol kg-1 or 0.56 molal

A complex ion is an ion which has a central metal or metal ion coordinated by molecules or
negative ions, known as ligands. In [Cu(NH3)4]2+, ammonia (NH3) can form a coordinate bond
by donating its lone pair of electrons on the nitrogen atom to the empty valence-shell orbitals of
the Cu2+ ion. Four NH3 molecules can thus coordinate to a Cu2+ ion and form a [Cu(NH3)4]2+ ion
as shown below.

Cu(NH3)4]2+ ion

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The name of [Cu(NH3)4]2+ ion is determined as follows:

The complex is a positively charged species, therefore it name will be end with ion. The central
metal ion is Cu2+, it will have copper(II) in its name. Note that since it is a positively charged
complex ion, the name of the metal is written as copper. The ligand is ammonia (NH3).
Therefore, the ligand will be named as ammine. Note the double m in ammine. Since there are
four NH3 ligands, the name will have tetraammine in its name. The coordination number of the
complex ion is also 4 because of this reason.The name of the complex ion will be
tetraamminecopper(II) ion. Note that there is no space between the name of the ligand and metal.

Another example is naming of [Cu(Cl)4]2- ion as described below:

The complex is a positively charged species, therefore it name will be end with ion.The central
metal ion is Cu2+, it will have cupric(II) in its name. Note that since it is a negatively charged
complex ion, the name of the metal is written as cupric. The ligand is chloride ion (Cl).
Therefore, the ligand will be named as chloro. Since there are four NH3 ligands, the name will
have tetrachloro in its name. The coordination number of the complex ion is also 4 because of
this reason.
The name of the complex ion will be tetrachlorocupric(II) ion.

Another example is naming of [Cu(H2O)6]2+ ion as described below:

The complex is a positively charged species, therefore it name will be end with ion. The central
metal ion is Cu2+, it will have copper(II) in its name. Note that since it is a positively charged
complex ion, the name of the metal is written as copper. The ligand is water (H2O). Therefore,
the ligand will be named as aquo. Since there are six NH3 ligands, the ion will have hexaaquo in
its name. The coordination number of the complex ion is also 6 because of this reason.

The name of the complex ion will be hexaqauocopper(II) ion. It as an example of an octahedral
complex, because the six ligands coordinate to the Cu2+ ion forming an octahedron (a solid with
eight identical faces), as shown below.

Source: http://www.linux-host.org

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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.

For example, water (NH3) can form a coordinate bond by donating its lone pair of electrons on
the nitrogen atom to the empty valence-shell orbitals of the Cu2+ ion. Four NH3 molecules can
thus coordinate to a Cu2+ ion and form a [Cu(NH3)4]2+ ion as shown below.
[Cu(NH3)4]2+ is a square planar complex.

Ammonia molecule [Cu(NH3)4]2+ ion

Sodium oxide (Na2O) will have ionic bonding. This is because sodium is a highly electropositive
metal and it will lose its valence electron to the highly electronegative oxygen (a non-metal), so
that both the atoms obtain a full and stable octet.

The atomic number of sodium is 11 and its electronic configuration is 1s22s22p63s1.


The atomic number of oxygen is 8 and its electronic configuration is 1s22s22p4.

Since Na has only one valence electron (3s1), two Na atoms will have to lose two valence
electrons to an O atom, which will gain the two electrons to obtain a full octet. The ions form
will be Na+ and O2-.

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The percentage ionic character in Na2O can be determined:

% ionic character = (Electronegativity difference / larger electronegativity value) x 100 %

= (Electronegativity value of oxygen - Electronegativity value of oxygen) x 100%


Electronegativity value of oxygen

= (3.5 - 0.9) x 100% = 74.3%


3.5

Na2O will react with water to form sodium hydroxide solution, which is basic because of
hydroxide ions. Sodium hydroxide is a strong base and will dissociate into Na+ and OH- ions in
aqueous solutions.

Na2O(s) + H2O(l) → 2NaOH(aq)

NaOH(aq) → Na+(aq) + OH-(aq)

Phosphorous pentoxide (P2O5) is a simple molecular compound and reacts with water to form
phosphoric acid.

P2O5(s) + 3H2O(l) → 2H3PO4(aq)

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The above equation is incorrect. Note that the corrected equation is as follows:

C2H6(g) + Cl2(g) → C2H5Cl(g) + HCl(g)

Or

H H H H
H C C H + Cl Cl H C C Cl + HCl

H H H H
ethane chlorine chloroethane hydrogen chloride

The above is an example of a substitution reaction. A Cl atom has substituted a H atom in C2H6.

For that to happen, 1 mole of Cl-Cl and 1 mole of C-H bond will break to form 1 mole of C-Cl
and 1 mole of H-Cl bond.

Energy absorbed for bond breaking = Cl-Cl bond energy + C-H bond energy

= 242 kJ mol-1 + 413 kJ mol-1

= 655 kJ mol-1

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Energy released from bond formation = C-Cl bond energy + H-Cl bond energy

= 339 kJ mol-1 + 431 kJ mol-1

= 770 kJ mol-1

Therefore,

Enthalpy change for the reaction (∆H):

= Energy absorbed for bond breaking - Energy released from bond formation

= 655 kJ mol-1 - 770 kJ mol-1

= -115 kJ mol-1

∆H =-115 kJ mol-1, which means that 115 kJ mol-1 of energy was released to the surroundings
from the reaction.

Therefore, is classified as an exothermic reaction.

The parent chain is propan-1-ol. The second carbon will have a methyl group.
H CH3 H
H C C C OH
H H H

2-methylpropan-1-ol

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Compare the structures of both compounds:

H CH3 H H H O
H C C C OH H C C C O CH3
H H H H H
2-methylpropan-1-ol methyl propanoate

2-methylpropan-1-ol 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-methylpropan-1-ol will
form hydrogen bonds with water molecules and therefore will be more soluble in water. On the
other hand methoxyethane (methylethylether) 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.

Another similar example using ethanol and dimethylether is illustrated below. One molecule of
ethanol can form two hydrogen bonds with ne two water molecules, while one dimethylether
molecule can only form one hydrogen bond with a water molecule.

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C2H5Cl or chloroethane (an alkyl halide or haloalkane) has a chlorine atom, which is highly
electronegative, on the first carbon atom. This carbon atom is thus slightly positive and can be
attacked by a nucleophilic species. Ammonia (NH3) is a nucleophile. Therefore NH3 will attack
the carbon bonded to chlorine atom and make the chlorine atom leave as a chloride ion. The
product will be ethanamine. The reaction will be as follows:

The reaction is shown below:

H H H H
alcohol
H C C Cl
+ NH3 H C C NH2 + HCl
H H H H
chloroethane ammonia hydrogen chloride
ethanamine

It has the C-N bond, hence it belongs to the amine/alkanamine/aminoalkane group of


compounds.

It is a primary (1˚) amine, because the nitrogen atom is attached to one carbon atom or one alkyl
group and two hydrogens.

For a secondary (2˚) amine, the nitrogen atom is attached to two carbon atoms or two alkyl
groups and one hydrogen.
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For a tertiary (3˚) amine, the nitrogen atom is attached to three carbon atoms or three alkyl
groups.

The difference between primary, secondary and tertiary amines are illustrated below (note that R
is any alkyl group):

Example:

This example is based on the Hess’s law. Hess’s law state that energy (enthalpy) changes in
chemical reactions are the same, regardless whether the reactions occur in one or several steps.

The standard enthalpy or heat of formation (ΔHf˚) 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.

The equation for the heat of formation (ΔHf) of CS2 is given:

C(s) + 2S(s) → CS2(l)

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The heat of combustion of the three substances (C(s), S(s),and CS2(l)) are given, which
can be used to calculate the standard enthalpy or heat of formation (ΔHf˚) of CS2.

The three equations need to be added in such a way so that the equation for the ΔHf˚of CS2 is
obtained.

To do this,

(i) Leave the first equation as it is, because C(s) is the reactant and only one mole is involved.

C(s) + O2(g) → CO2(g) ΔH = -393 kJ

(ii) The second equation needs to be multiplied by 2 so that we have 2S(s) as the reactant (the
ΔH˚ is also multiplied by 2):

( S(s) + O2(g) → SO2(g) ΔH˚ = -297 kJ mol-1 ) x 2

2S(s) + 2O2(g) → 2SO2(g) ΔH = -594 kJ

(ii) The third equation needs be reversed so that we have CS2 (s) as the product (the sign on the
ΔH˚ is also reversed):

CO2(g) + 2SO2(g) → CS2(l) + 3O2(g) ΔH = +1007 kJ

(iv) Adding all the equations together gives:

C(s) + O2(g) + 2S(s) + 2O2(g) + CO2(g) + 2SO2(g) → CO2(g) + 2SO2(g) + CS2(l) + 3O2(g)

ΔH = (-393 kJ) + (-594 kJ) + (1007 kJ) = +20 kJ

(v) Simplifying the above equation by canceling out the like terms gives:

C(s) + 2S(s) → CS2(l)

The standard enthalpy or heat of formation (ΔHf˚) of CS2(l) is +20 kJ mol-1.

Sodium nitrate (NaNO3) solution:


Volume = 1.00 L ; Concentration = 0.100 mol L-1

Calcium nitrate (Ca(NO3)2) solution:


Volume = 1.00 L ; Concentration = 0.100 mol L-1

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Total volume of solution = 1.00 L + 1.00 L = 2.00 L

1 mole of NaNO3 dissociates into 1 mole of Na+ and 1 mole of NO3- ions in solution.

NaNO3 → Na+ + NO3-

Therefore, total moles of NO3- ions from NaNO3 solution = total moles of NaNO3 in solution
= Concentration x Volume
= 0.100 mol L-1 x 1.00 L
= 0.100 mol

1 mole of Ca(NO3)2 dissociates into 1 mole of Ca2+ and 2 moles of NO3- ions in solution.

Ca(NO3)2 → Ca2+ + 2NO3-

Therefore, total moles of NO3- ions from Ca(NO3)2 solution = Concentration x Volume
= 2 x (0.100 mol L-1 x 1.00 L)
= 0.200 mol

Concentration of NO3- ions in the final solution = Total moles of NO3- ions in the solution
Total volume of the solution

= 0.100 mol + 0.200 mol


2.00 L

= 0.15 mol L-1

Note that the standard reduction potentials (SRP) of redox couples are given, which indicate the
ease with which each metal ion will reduce to metal. The more positive the SRP, the easier for
the metal ion to reduce to metal. Out of the five redox couples, Ag/Ag+ has the most positive
SRP (+0.80 V), which means that Ag+ ions will reduce most easily. In other words, Ag+ ions has
the most potential to oxidise a substance. Therefore, Ag+ is the strongest oxidising agent of all.

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The best approach to this is to take the redox couple with the most positive SRP and combine it
with the redox couple with the most negative SRP.

In that case the following will be combined:

Ag+/Ag +0.80 V (More positive potential, hence Ag+ will reduce to Ag)

Mg2+/Mg -2.32 V (Mg will oxidise to Mg2+)

Calculating the maximum cell emf for a cell made by combing the above two redox couples:

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 Ag+ is being reduced to Ag, while Mg is oxidised to Mg2+,
E˚cell = E˚(Ag+/Ag) - E˚(Mg2+/Mg)
= 0.80 V – (-2.32 V)
= +3.12 V

It can be shown that the combination of two redox couples from the list in any other way will not
give the maximum cell emf, i.e. the cell emf will not be greater than +3.12 V.

OR

Another less preferred and much longer approach to this problem is to make all possible
combinations of the redox couples from the list and see which pair of couple give the maximum
cell emf.

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SECTION C

Average atomic mass of boron = Σ (% abundance of isotope x Ar of isotope)


100

= 19.8 x 10.0129 + 80.2 x 11.0093


100 100

= 1.9826 + 8.8295

= 10.81 (rounded off to 2 decimal places)

(i) The Principal Quantum Number describes the main energy levels or the size of the shell.
A summary of all types of quantum numbers is given in the table below:

Source: http://ftp.stmarys-ca.edu/jsigman/Chem130/assignments/atomic-structure/quantum-numbers.htm

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(ii) Shape of p-orbitals are shown below. All three p-orbitals have the same shape (dumb bell,
eight, peanut or infinity shape) but have different orientations in space.
2pz is oriented along the z –axis, 2px is oriented along the x –axis and 2py is oriented along the y –
axis .

(iii) Note that an s subshell has one orbital and can only accommodate a maximum of 2
electrons, a p orbital has three orbitals and can accommodate a maximum of 6 electrons and a d
subshell has five orbitals and can accommodate 10 electrons.

Subshell No. of orbitals Box representation Maximum no. of


electrons

s 1 1

p 3 6

d 5 10

1. Start with calculating the total number of valence electrons in CO32- ion:

1 x C = 1 x 4 e- = 4 e-
3 x O = 3 x 6 e- = 18 e-
-2 charge = 2 e-
Total = 24 valence electrons or 12 electron pairs

2. Place the C atom in the center and O atoms equally spaced around it.

o
o C
o
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3. Place a pair of electrons between all the atoms to at least form a bond.

o
o C
o
4. Since 6 electrons have been used up, 18 electrons are left. Place these as lone pairs around
atoms which need an octect. In other words, all the atoms still need more electrons to obtain an
octect. Place the 18 electrons around the three O atoms.

o
o C
o
5. After all the 24 valence electrons have been used up, it is evident that the carbon atom is still
without an octect. Therefore one of the oxygen atoms has to further donate a pair of electrons to
form a bond with carbon (a double bond between carbon and oxygen will result).

o
o C
o
6. All the 24 valence electrons have been used up, and all the atoms have an octect. Place square
brackets ([ ]) around the structure and indicate the -2 charge on the ion.
Therefore we have arrived to the Lewis structure of CO32-. This answer is acceptable at this level.
2-
o
o C
o

Note: The above Lewis structure is not the only one possible for CO32-. The double bond with
carbon can be by formed by any of the three oxygen atoms. 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.

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Shape of CO32- ion:

Since there are 3 sets of bonded electron pairs (2 single and 1 double bonded electron pairs) only,
they will equally repel each other and space around the carbon atom at a maximum of 120˚ to
attain a trigonal planar shape.

The atomic number of nickel is 28. Its electronic configuration is 1s22s22p63s23p64s23d8. Its box
orbital diagram will be:

1s 2s 2p 3s 3p 4s 3d

It is evident that the 3d orbital has two unpaired electrons. It is these unpaired electrons which
gives rise to paramagnetism in metals. Paramagnetic metals will be attracted by a magnetic field.
Metals which have all electrons paired up will be diamagnetic and not attracted by a magnetic
field.

The water molecules, through its oxygen atom, donate a pair of electrons to the Si atom in SiCl4.
Or, the silicon uses it vacant orbitals in bonding with water molecules.

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(i) Pressure of O2 = P – SVP of water = 101.3 kPa – 2 kPa = 99.3 kPa

(ii) STP (Standard Temperature and Pressure) is 0 ˚C or 273 K and 1 atm or 101.3 kPa

P1 = 99.3 kPa P2 = 101.3 kPa


V1 = 30 mL V2 = Volume at STP =?
T1 = 20 ˚C = 293 K T2 = 0 ˚C = 273 K

P1 V1 / T1 = P2 V2 / T2 or V2 = P1 V1 T2 / T1 P2

= (99.3 kPa) (30 mL) (273 K) / (101.3 kPa) (293 K)

V2 = 27.40 mL (2 decimal places)

(iii) To find the moles or mass of O2 produced in the experiment, the ideal gas equation, PV=
nRT, or PV = mRT/M, respectively, can be used.

Using PV= nRT or n = PV/RT

Pressure of O2 = P – SVP of water = 101.3 kPa – 2 kPa = 99.3 kPa


Volume of O2 = V = 30 mL = 0.03 L
R = 8.314 J K-1 mol-1
T = 20 ˚C = 293 K
Moles of CO2 = n = ?

n = PV/RT
= (99.3 kPa) (0.03 L) / (8.314 J K-1 mol-1) (293 K)
n = 1.22 x 10-3 mol

Mass of O2 =nxM
= 1.22 x 10-3 mol x 32 g mol-1
= 0.04 g (Answer rounded off to 2 decimal places)

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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 or m = PVM/RT

Pressure of O2 = P – SVP of water = 101.3 kPa – 2 kPa = 99.3 kPa


Volume of O2 = V = 30 mL = 0.03 L
R = 8.314 J K-1 mol-1
T = 20 ˚C = 293 K
Molar mass of O2 = M = 32 g mol-1
Mass of O2 = m = ?

m = PVM/RT

= (99.3 kPa) (0.03 L) (32 g mol-1) / (8.314 J K-1 mol-1) (293 K)

m = 0.04 g (Answer rounded off to 2 decimal places)

(i) 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)

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Graph I

Graph I is for magnesium chloride (MgCl2) solution. MgCl2 is a strong electrolyte and will
dissociate completely in aqueous solution (0.1 mol is taken as an example to compare the
amounts of different species present). Note that one mole of MgCl2 dissociates into 1 mole of
Mg2+ and 2 moles of Cl-. That is why 0.1 mole of MgCl2 dissociates into 0.1 mole of Mg2+ and
0.2 moles of Cl-.

MgCl2(s) → Mg2+ (aq) + 2Cl-(aq)


0.1 mol 0.1 mol 0.2 mol

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:

[H3O+] = [OH-] = 1 x 10-7 mol L-1

Therefore, the species present in the solution of magnesium chloride solution will be Mg2+, Cl-,
H2O, 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-] = 0.2 mol L-1

[Mg2+] = 0.1 mol L-1

[H3O+] = [OH-] = 1 x 10-7 mol L-1

When placed in order, the list of species in Graph I, with decreasing concentrations will be:

[H2O] > [Cl-] > [Mg2+] > [H3O+] = [OH-]


A C B D E

(ii) Graph II

Graph II is for ethanoic acid solution. CH3COOH is a weak acid and will dissociate partially and
to a small extent (about 1-3%) in water as shown below (0.1 mol is taken as an example to
compare the amounts of different species present). Ethanoic acid reacts with the water in a
reversible fashion to form hydronium and ethanoate ions.

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CH3COOH(l) → CH3COOH(aq)
0.1 mol 0.1 mol

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)


0.1 mol - x x mol x mol

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:

[H3O+] = [OH-] = 1 x 10-7 mol L-1

However, the ethanoic acid solution is acidic due to the increased H3O+ concentration as shown
in the equation above: CH3COOH(aq) + H2O(l) CH3COO-(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 ethanoic acid solution will be H2O, CH3COOH,
CH3COO-, 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

[CH3COOH] ≈ 0.1 mol L-1

1 x 10-7 mol L-1 < [CH3COO-] < 0.1 mol L-1

1 x 10-7 mol L-1 < [H3O+] < 0.1 mol L-1

[H3O+] = [CH3COO-]

[OH-] < 1 x 10-7 mol L-1


When placed in order, the list of species in Graph II, with decreasing concentrations will be:

[H2O] > [CH3COOH] > [CH3COO-] = [H3O+] > [OH-]


A B C D E

Or

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[H2O] > [CH3COOH] > [H3O+] = [CH3COO-] > [OH-]


A B C D E

(iii) Magnesium chloride will be a better electrolyte because it dissociates completely in aqueous
solution, while ethanoic acid only dissociates partially. The aqueous solution of magnesium
chloride will have greater number of ions in solution for electrical conductivity as compared to
ethanoic acid.

Split the above ionic equation into two half-equations.

The half-equations would be as follows:

MnO4- → Mn2+
C2O42- → CO2

It is not important here to identify the oxidation reduction half-equations, as they would be
become evident as they are being balanced. However, it would be a good practice to identify
them before balancing them so that it can assist in verifying the balanced half-equations.

Deduce the oxidation and reduction half-equations from the ionic equation above.

Reduction half-equation

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

Balance the reduction half-equation:

MnO4- → Mn2+
Mn atoms are balanced as it is.

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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 is now balanced.

Oxidation half-equation

The oxidation half-equation is: C2O42- → CO2

It can be shown that the oxidation state of C is +3 in C2O42-, which increases to +4 in CO2.

C2O42- → CO2

2C + 4(O) = -2 C + 2(O) = 0
2C + 4(-2) = -2 C + 2(-2) = 0
2C - 8 = -2 C-4=0
2C = 6 C=0+4
C = +3 C = +4

Therefore, balance the oxidation half-equation:

C2O42- → CO2

Balance the number of C on both sides by having 2 moles of CO2:

C2O42- → 2CO2
There are 2 C on both sides now.
There 4 O atoms on both sides, so water is not added.
There is no need to add any H+ either.

On the left, the total charge is -2, but on the right, the total charge is zero.

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Balance the charges on both sides by adding 2 electrons on the right hand side.

C2O42- → 2CO2 + 2e-

There is a total charge of zero on both sides now.

The oxidation half-equation has been balanced.

Balancing the equation in acidic medium:

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.

5e- + 8H+ + MnO4- → Mn2+ + 4H2O

C2O42- → 2CO2 + 2e-

Since we have 5e- and 2e-, the common multiple for 4 and 5 would be 10.
Therefore multiplying the first equation by 2 and the second equation by 5 will result in 10e- in
both half-equations as follows:

(5e- + 8H+ + MnO4- → Mn2+ + 4H2O) x 2

(C2O42- → 2CO2 + 2e-) x 5

After multiplication:
10e- + 16H+ + 2MnO4- → 2Mn2+ + 8H2O

5C2O42- → 10CO2 + 10e-

Adding the above two equations will give:

10e- + 16H+ + 2MnO4- + 5C2O42- → 2Mn2+ + 8H2O + 10CO2 + 10e-

Canceling out the e- will result in the final balanced equation in acidic medium:

16H+ + 2MnO4- + 5C2O42- → 2Mn2+ + 8H2O + 10CO2

Including the physical states of the reactants and products, the equation will be as follows:

16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq) → 2Mn2+(aq) + 8H2O(l) + 10CO2(g)

The equation has been balanced in acidic medium.

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O
O 6
1
5 OH
OH 2
4
3
OH

benzoic acid
2-hydroxybenzoic acid

There are carboxylic (COOH) and hydroxyl (OH) groups on the benzene ring. The carboxylic
group (COOH) is of higher priority than the hydroxyl group (OH). Therefore the carbon atom
having the carboxylic group will be number 1 and compound will be named as a carboxylic acid.
The hydroxyl group will be treated as a substituent at the second carbon (2-hydroxy). Therefore
the name of the compound will be 2-hydroxybenzoic acid.

Since the carboxylic (COOH) and (OH) hydroxyl groups are in ortho (o) position (1 and 2
positions), the name of the compound can also be o-hydroxybenzoic acid. See examples of meta
(m) (1 and 3 positions) and para (p) (1 and 4 positions) compounds of hydroxybenzoic acid.

O O
O 6
6
6 1
1 5
1 5 OH OH
5 OH
2 4 2
2 4
4 HO 3
3
OH 3
OH

o-hydroxybenzoic acid m-hydroxybenzoic acid p-hydroxybenzoic acid

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The empirical formula mass of C3H6O2 is:

3C + 6H + 2O = (3 x 12) + (6 x 1) + (2 x 16) = 36 + 6 + 32 = 74 g mol-1.

The molecular mass of C3H6O2 is 74 g mol-1.

Since the empirical formula mass of C3H6O2 is same as its molecular mass, the molecular
formula of the compound is same as its empirical formula, i.e. molecular formula is C3H6O2.

Structural isomers are molecules which have the same molecular formula but have different
connectivities or bonding arrangement among atoms. C3H6O2 can have three structural isomers:

H H O H O O
H C C C H C C H C
H H OH H O CH3 O CH2 CH3

C3H6O 2 C3H6O 2 C3H6O 2


propanoic acid methyl ethanoate ethyl methanoate

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45

(i) The given curve is for a weak acid and a strong base titration. A strong base is added to a
weak acid during the titration.

Acid-base titration curves

Strong acid – strong base (alkali) e.g. HCl(aq) and NaOH(aq)

When adding acid to base (alkali): When adding base (alkali) to acid:

Source: http://www.chemguide.co.uk/physical/acidbaseeqia/phcurves.html

Strong acid – weak base (alkali) e.g. HCl(aq) and NH3(aq)

When adding acid to base (alkali): When adding base (alkali) to acid:

Source: http://www.chemguide.co.uk/physical/acidbaseeqia/phcurves.html

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Weak acid – strong base (alkali) e.g. CH3COOH(aq) and NaOH(aq)

When adding acid to base (alkali): When adding base (alkali) to acid:

Source: http://www.chemguide.co.uk/physical/acidbaseeqia/phcurves.html

Weak acid – weak base (alkali) e.g. CH3COOH(aq) and NH3(aq)

When adding acid to base (alkali): When adding base (alkali) to acid:

Source: http://www.chemguide.co.uk/physical/acidbaseeqia/phcurves.html

(ii) To find the pKa, find the mid-point, which is located in the center of the buffer region. This is
geometrically halfway between the equivalence point and the beginning of the titration. The
midpoint determines the pKa of the acid. Therefore, pKa ≈ 4.2 or 4.3 (See arrow below).

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(ii) To find pH at end point, find the equivalence point, which is the steepest part of the curve
where the pH rises the fastest. Therefore, pH at end point ≈ 8.3 or 8.4 (See arrow below).

(iii) Out of the four indicators, phenolphthalein’s pKa value is the closest to the pH value at the
equivalence point. Phenolphthalein’s pKa value is 9.6, while the pH value at the equivalence
point is around 8.3. Therefore phenolphthalein can be suitable used to indicate the colour change
at the end point of the titration or to approximate the equivalence point of the titration.

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Finding Equivalence Point using Geometric Method (Weak acid – strong base titration)

Finding Mid Point using Geometric Method (Weak acid – strong base titration)

Source:

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The hydration reaction is shown below:

H3C H OH H
H2O
C C H3C C C H
H H H H
propene propan-2-ol

This is an example of Markonikov’s addition, whereby the H adds to the carbon which is already
enriched with hydrogen and OH gets added to the other carbon atom.

H3C H
C C
H H

The double bonded carbon on the left has a CH3 group and H attached to it. The double bonded
carbon on the right has two Hs attached to it. Therefore the incoming H will attach to the double
bonded carbon on the right. OH will attach to the double bonded carbon on the left.

H H
C C
H H

The reactant is ethene. It is symmetrical. The double bonded carbon on the left has two
hydrogens attached to it. The double bonded carbon on the right has two hydrogens attached to it
as well. Therefore both the carbons have equal number of hydrogens and will not show
preference for the incoming hydrogen.
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If the H gets attached on the left carbon and the OH on the right carbon, ethanol will result as a
product.
If the H gets attached on the right carbon and the OH on the left carbon, ethanol will again result
as a product.
H H H H
H C C H H C C H
H OH OH H
ethanol ethanol

Potassium chloride (KCl) solution:


Volume = 75 mL = 0.075 L; Concentration = 0.002 mol L-1

Silver nitrate (AgNO3) solution:


Volume = 25 mL = 0.025 L; Concentration = 0.005 mol L-1

Total volume of solution = 0.075 L + 0.025 L = 0.10 L

Ionic equation:

KCl dissociates K+ and Cl- ions in solution. KCl(s) → K+(aq) + Cl-(aq)


AgNO3 dissociates into Ag+ and NO3- ions in solution. AgNO3(s) → Ag+(aq) + NO3-(aq)

KCl(aq) + AgNO3(aq) → AgCl(s) + KNO3(aq)

K+(aq) + Cl-(aq) + Ag+(aq) + NO3-(aq) → AgCl(s) + K+(aq) + NO3-(aq)

Net ionic equation (cancel out the spectator ions):

Cl-(aq) + Ag+(aq) → AgCl(s)

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Potassium chloride (KCl) solution:


Volume = 75 mL = 0.075 L; Concentration = 0.002 mol L-1
KCl dissociates K+ and Cl- ions in solution. KCl(s) → K+(aq) + Cl-(aq)

Therefore, total moles of Cl- ions from KCl solution


= total moles of KCl in solution
= Concentration x Volume
= 0.075 mol L-1 x 0.002 L
n = 1.5 x 10-4 mol

Concentration of Cl- ions in the final solution = Total moles of Cl- ions in the solution
Total volume of the solution

= 1.5 x 10-4 mol


0.100 L

[Cl-] = 1.5 x 10-3 mol L-1

Silver nitrate (AgNO3) solution:


Volume = 25 mL = 0.025 L; Concentration = 0.005 mol L-1
AgNO3 dissociates into Ag+ and NO3- ions in solution. AgNO3(s) → Ag+(aq) + NO3-(aq)

Therefore, total moles of Ag+ ions from AgNO3 solution


= total moles of AgNO3 in solution
= Concentration x Volume
= 0.025 mol L-1 x 0.005 L
n = 1.25 x 10-4 mol

Concentration of Ag+ ions in the final solution = Total moles of Ag+ ions in the solution
Total volume of the solution

= 1.25 x 10-4 mol


0.100 L

[Ag+] = 1.25 x 10-3 mol L-1

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Firstly, the ionic product of AgCl has to be found:


IP (AgCl) = [Ag+] × [Cl-]
= 1.25 x 10-3 mol L-1 × 1.5 x 10-3 mol L-1
= 1.875 × 10-6 mol2 L-2
= 1.88 × 10-6 mol2 L-2

Compare the ionic product (IP) and Ksp of AgCl:

Since IP (1.875 × 10-4) > Ksp (1.7 x 10-10), a precipitate will form.

The standard enthalpy (heat) of combustion carbon (C) and the standard enthalpy (heat) of
formation of carbon dioxide (CO2) release the same amount of energy because they involve the
same equation. The equation involves one mole of carbon (C) reacting with one mole of oxygen
(O2) to give one mole of carbon dioxide (CO2) under standard state conditions.

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It can be seen that Br2 is being reduced to Br-, while Fe2+ is oxidised to Fe3+.

If the standard reduction potentials (E˚) of the two half-cells are compared, then it is obvious that
the standard reduction potential of the Br2/Br-couple is more positive (or larger) than the standard
reduction potential of the Fe3+/Fe2+ couple.
i.e. +1.09 V > +0.77 V.

This implies that Br2 can be more easily reduced to Br- as compared to Fe3+ being reduced to
Fe2+. As such, Br2 will be reduced to Br-, while Fe2+ will be oxidised to Fe3+, which confirms that
the above reaction will occur spontaneously.

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 Br2 is being reduced to Br- and Fe3+ is being oxidised to
Fe3+:
E˚cell = E˚red - E˚oxd
= E˚(Br2/Br-) - E˚(Fe3+/Fe2+)
= 1.09 V – 0.77 V
= +0.32 V

Since the E˚cell is positive, it confirms that the above reaction will occur spontaneously.

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(i)

O O
+ NaOH +
H3C CH2 C H3C CH2 C CH3OH
O CH3 ONa

(ii) The Na+ from NaOH substitutes the methyl (CH3) group in the ester to form sodium
propanoate and the methyl combines with the hydroxide ion from NaOH to form methanol.

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(i) Compound C
Compound B, C2H5OH or ethanol (an alcohol) is reacted with CH3COCl or ethanoyl chloride (an
acyl chloride). C2H5OH is a nucleophile in this reaction.

Acid chlorides react with 1° alcohols and 2° alcohols to form esters.

Therefore, this will be a nucleophilic addition / elimination reaction, where ethyl ethanoate and
hydrogen chloride will form. The major product, Compound C, would be ethyl ethanoate.

The reaction is shown below:


O O
H3C CH2 OH
+ H3C C H3C C + HCl

Cl O CH2 CH3
C2H5OH CH 3COCl CH 3COOCH 2CH 3
ethanol ethanoyl chloride ethyl ethanoate hydrogen chloride

Compound D
Compound A, C2H4 or ethene (an alkene), will react with hydrogen (H2) with nickel catalyst (Ni)
to form Compound D, which is ethane (C2H6). This type of reaction is an addition or
hydrogenation reaction. The addition or hydrogenation reaction is shown below:

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H H H2 / Ni H H
C C H C C H
H H H H

C2H4 C2H6
hydrogen with Ni catalyst
ethene ethane

(ii) Reagent X

Compound A, C2H4 or ethene (an alkene), can be reacted with a strong oxidising agent to form
carbon dioxide (CO2) and water (H2O). Therefore Reagent X could be acidified potassium
permanganate (KMnO4/H+) or oxygen (O2).

The reaction is:

+ +
H H KMnO4/H O KMnO4/H
C C H C O C O + H 2O

H H OH

C2 H4 HCOOH CO 2
ethene methanoic acid carbon dioxide water

Or
H H O2
C C O C O + H2 O
H H

C2H4 CO 2

ethene carbon dioxide water

Reagent Y

Compound B, C2H5OH or ethanol (an alcohol) can be reacted with acidified potassium
dichromate (K2Cr2O7/H+), which is a strong oxidising agent. This will result in the oxidation of
ethanol to ethanoic acid or CH3COOH. Therefore Reagent Y is K2Cr2O7/H+. 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

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Compound B, C2H5OH or ethanol (an alcohol) can be converted to Compound A, C2H4 or ethene
(an alkene). This will be a dehydration reaction. Water (H2O) is eliminated from C2H5OH to give
a double bond between the two carbon atoms. This can be achieved by using concentrated
sulphuric acid under heated conditions.

The dehydration reaction is shown below:

H H H H
H C C OH conc. H2SO4 + heat C C + H2 O

H H H H

bromoethane ethene water

Limiting reagent is the reactant which is completely used up in the reaction or the reactant which
limits the amount to products being formed in reaction.

To find that, the moles of each reactant can be calculated and compared using the mole ratio.

Moles of Zn = m/A = 30/65 = 0.46 mol

Moles of S = m/A = 36/32 = 1.13 mol.

Moles of Zn is less than moles of S.

Mole ratio

Zn : S

1:1

Since the mole ratio is 1 : 1, it means that 1 mole of Zn will combine with 1 mole of S to give 1
mole of ZnS. Based on the amounts of reactants given, 0.46 moles of Zn will combine with 0.46
moles of S to form 0.46 moles of ZnS. In other words, Zn will be completely used up and is
therefore the limiting reagent. On the other hand, 0.67 moles of S is in excess and will remain
unreacted in the reaction.

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Compare the structures of the above two compounds:

H H H H
H C C OH H C O C H
H H H H

ethanol dimethyl ether

Ethanol 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. Ethanol molecules will readily form hydrogen bonds
between each other. On the other hand dimethyl ether does not have an OH group and does not
have the ability to form hydrogen bonds between its molecules. As a result intermolecular forces
between the dimethyl ether molecules will be weaker and more easily overcome as compared to
the relatively stronger hydrogen bonds in ethanol.

Hydrogen bonding in liquid ethanol:

Source: http://socratic.org/

THE END

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