Instructions:

Revise this set of notes, complete all the exercises in the notes. Check the answers on the
google drive.
Victoria Junior College

2022 H2 Chemistry Revision for Promo Exam

Part A: Overview
1. Chemical of Semester 2 Topics
Equilibria

1. Acid-Base Equilibria

(I) Overview
1. Theories of Acids and Bases [Understand + Apply]

Bronsted-Lowry Theory
Acid: proton donor Base: proton acceptor
H2O (l) + NH4+ (aq) ⇌ NH3 (aq) + H3O+ (aq) H2O (l) + NH3 (g) ⇌ NH4+ (aq) + OH- (aq)
Base Acid Conjugate Conjugate Acid Base Conjugate Conjugate
base of NH3 acid of H2O acid of NH3 base of H2O

*Conjugate acid-base pairs differ by only 1 proton, H+.

 Acid dissociation constant, Ka: Measure of the  Base dissociation constant, Kb: Measure of
strength of acid (tendency of acid to the strength of base (tendency of base to
dissociate into ions) dissociate into ions)
For partial dissociation of weak acid, HA: For partial dissociation of weak base, B:
HA(aq) + H2O(l) ⇌ H3O+ (aq) + A-(aq) For B(aq) + H2O(l) ⇌ BH+(aq) + OH-(aq)
At eqm, [HA] >> [H3O+] = [A] At eqm, [B] >> [BH+] = [OH]
[ H 3O  ][ A ] [BH  ][OH  ]
Ka = (unit: mol dm-3) & pKa = –lg Ka Kb = (unit: mol dm-3) & pKb = –lg Kb
[ HA] [B ]
[H3O+] = [A] = (Ka.c)1/2 [OH] = [BH+] = (Kb.c)1/2
pH = –lg[H3O+] = –lg (Ka.c)1/2 where c = [HA]initial pOH = –lg[OH] = –lg (Kb.c)1/2 where c = [B]initial
**Larger the Ka (or smaller the pKa), stronger the **Larger the Kb (or smaller the pKb), stronger the
acid and vice versa. base and vice versa.
**Note:
 pH is not a good measure for the strength of an acid or a base since its value changes with concentration
and degree of dissociation.
 Hence, a more reliable method of measuring the strength of an acid or base is to use its dissociation
constant, Ka or Kb.
 Ka (or Kb) is a constant for a particular acid (or a particular base) at all concentrations and is
influenced only by temperature changes.

Lewis Theory
Acid: electron pair acceptor Base: electron pair donor
BF3 + :NH3  F3B  :NH3
Lewis acid Lewis base

Arrhenius Theory
Acid: A compound or element that releases Base: A compound or element that releases
hydrogen (H+) ions into the solution. hydroxide (OH-) ions into the solution.
e.g. HNO3 (aq)  H+(aq) + NO3-(aq) e.g. LiOH(aq)  Li+(aq) + OH-(aq)

1
2. Self-ionisation of Water [Understand + Apply]
For self-ionisation of water, H2O(l) ⇌ H+ (aq) + OH (aq), ∆H > 0 (endothermic process)
 At 25oC, for pure water, [H+] = [OH] = 10-7 mol dm-3,
Kw = [H+][OH-] = 1.00 x 10-14 mol2dm-6  pKw = pH + pOH = 14
 At T > 25oC, self-ionisation of water will be favored since forward reaction is endothermic process,
[H+] = [OH-] > 10-7 mol dm-3, hence, pH < 7 and Kw > 1.00 x 10-14 mol2dm-6.
 However, water still remains neutral as long as [H+] = [OH-].

 For a conjugate acid-base pair,

Kw = Ka (acid) x Kb (conjugate base) = 1.00 x 10–14 mol2 dm-6 at 25oC  pKw = pKa + pKb = 14
e.g. Kw = Ka of NH4+ x Kb of NH3 = 1.00 x 10–14 mol2 dm-6
**Note: Ka, Kb and Kw are temperature-dependent, i.e. their values change with temperature.

3. Salt Hydrolysis (For soluble salt in water) & Acid-Base Indicators [Understand + Apply]

 When a salt dissolves in water, the resulting solution may be neutral, acidic or alkaline as it reacts with
water to some extent.

*SA: strong acid, SB: strong base

Suitable indicators
Type of
Nature of salt pH at equivalence pt used to detect the
neutralization
end-pt
Salt of SA–SB:
1. SA–SB Neutral No hydrolysis occurs, only hydration.
Any indicator
E.g.: HCl – NaOH Neutral solution obtained, i.e. pH = 7.
E.g.: Na+Cl
Full dissociation of salt in aq. soln: Methyl orange
NH4+Cl  NH4+ + Cl (pH working range of
Salt of SA–WB: indicator: 3.2 – 4.4)
2. SA–WB
Acidic Hydrolysis of NH4+ (strong conjugate
acid of weak base, NH3) occurs giving *Methyl orange
E.g.: HCl – NH3 an acidic solution (due to H3O+ changes colour from
E.g.: NH4+Cl
produced), i.e. pH < 7. yellow or red to
NH4+ + H2O ⇌ NH3 + H3O+ orange at end-point
Phenolphthalein
Full dissociation of salt in aq. soln: (pH working range of
CH3CO2Na+  CH3CO2 + Na+ indicator: 8.2–10)
3. WA–SB Salt of WA–SB:
Alkaline Hydrolysis of CH3CO2– (strong
conjugate base of weak acid, CH3CO2H) *Phenolphthalein
E.g.: changes colour from
occurs giving an alkaline solution (due
CH3CO2H – NaOH E.g.: CH3CO2Na+ colourless to pink or
to OH produced), i.e. pH > 7.
pink to colourless at
CH3CO2 + H2O ⇌ CH3CO2H + OH
end-point.

Salt of WA–WB: Undefined

4. WA–WB
undefined
Hydrolysis of CH3CO2– and NH4+ occur
No suitable indicator
E.g.: giving an acidic/alkaline/ neutral solution
E.g.:
CH3CO2H – NH3 (not important).
CH3CO2NH4+

2
For salts that contain small, highly charged cations

 AlCl3 completely ionises in solution: AlCl3(s) + 6H2O(l)  [Al(H2O)6]3+(aq) + 3Cl–(aq)

 Al3+ ion has high charge density and is highly polarising. Thus, [Al(H2O)6]3+ undergoes hydrolysis
as shown, i.e. it is able to attract/pull the electron cloud of H2O molecules towards itself and H3O+(aq)
ions are formed.
Al(H2O)63+ + H2O ⇌ Al(H2O)5(OH)2+ + H3O+
H H
H H
:O
H

:O
H H
H +
:O

H H
:O

:O
H
H :O
H Al3+ + H :O
:O :O H :O H H Al 3+ H
- H
:O :O
H H H
H
:O

:O
H H
H H
 In the presence of a base, Al(H2O)3(OH)3 is precipitated.
 Similar hydrolysis for other high charge density cations, Fe3+ and Cr3+ ions.

4. Buffer Solutions [Understand + Apply]

Weak acid buffer

Weak acid in water i.e. weak acid (HA) & its salt of a strong base (containing A–, the
conjugate base of HA)
HA(aq) ⇌ H+(aq) + A(aq)
How buffer works?

[ H  ][ A ] [ H  ]2 E.g.: A weak acid buffer containing CH3COOH & CH3COO-Na+:

Ka  
[ HA] [ HA] When a small amount of H+ (OH–) is added, it is removed by the large
reservoir of A– (HA) in the buffer. Thus, pH remains almost constant.
since [H+] = [A] When H+ is added: H+ + CH3COO  CH3COOH
When OH is added: OH + CH3COOH  CH3COO- + H2O

How to calculate pH of weak acid buffer?

HA(aq) ⇌ H+(aq) + A(aq) (Partial dissociatn of weak acid in aq. soln)
M+A(aq)  M+(aq) + A(aq) (Full dissociatn of salt in aq. soln)

[ H  ][ A  ] NOTE:
Ka  Majority of A comes from full dissociation of the
[ HA] salt, MA in aq. solution
[ H  ][ salt ]  [A] = [salt], [HA] = [HA]initial

[ HA] VERY IMPORTANT!  [H+]  [A]

Or, pH = pKa + lg ([salt]/[acid])

3
 Weak base buffer
Weak base in water i.e. weak base (B) & its salt of a strong acid (containing BH+, the
conjugate acid of B)
B(aq) + H2O ⇌ BH+(aq) + OH(aq)
How buffer works?

[ BH  ][OH  ] [OH  ]2 E.g.: A weak base buffer containing NH3 & NH4+Cl-:
Kb  
[ B] [ B] When a small amount of H+ (OH–) is added, it is removed by the large
reservoir of B (BH+) in the buffer. Thus, pH remains almost constant.
since [BH+] = [OH] When H+ is added: H+ + NH3  NH4+
When OH is added: OH + NH4+  NH3 + H2O

How to calculate pH of weak base buffer?

B(aq) + H2O ⇌ BH+(aq) + OH–(aq) (Partial dissociatn of weak base in aq.
soln)
BH+Cl–(aq)  BH+(aq) + Cl– (aq) (Full dissociatn of salt in aq. soln)

[ BH  ][OH  ] NOTE:
Kb  Majority of BH+ comes from full dissociation of
[ B] + –
the salt, BH Cl in aq. solution
[ salt ][OH  ]  [BH+] = [salt] and [base] = [base]initial

[ B] VERY IMPORTANT!  [BH+]  [OH]

Or, pOH = pKb + lg ([salt]/[base])

(II) Exercise

Question 1

1 Carbon dioxide plays a vital role in the chemistry of seawater. When atmospheric CO2 is dissolved
in seawater, H2CO3 is formed. H2CO3 is diprotic forming HCO3– and CO32– in the ocean.

The water of Lake Nakuru in the Kenyan rift valley contains dissolved sodium carbonate and sodium
hydrogencarbonate. The following equilibrium exists:

HCO3–(aq) ⇌ H+(aq) + CO32–(aq) Kc = 4.80 x 10–11 mol dm–3

(i) Explain with the aid of equations how this solution acts as a buffer on the addition of either
acid or alkali.

When a small amount of base is added,

HCO3–(aq) + OH–(aq) CO32–(aq) + H2O
Large reservoir of HCO3– in the buffer to remove the additional OH- ions and the
pH of the solution remains almost constant.

When a small amount of acid is added,

CO32–(aq) + H+(aq) HCO3–(aq)
Large reservoir of CO3 (aq) in the buffer to remove the additional H+ ions and
2–

the pH of the solution remains almost constant.

4
 [ ( )]
(ii) Calculate the pH of the water in Lake Nakura given that the ratio [ ( )]
is 0.958.
[ ][ ]
= [ ]
[ ][ ]
[ ] = [ ]
= (4.80 x 10–11)(1/0.958)
= 5.01 x 10–11 mol dm–3
pH = -lg (5.01 x 10–11)
= 10.3

(iii) When 10.0 cm3 of lake water was titrated with 0.20 mol dm-3 HCl, 22.0 cm3 of acid were
required to neutralize all the carbonate and hydrogencarbonate ions according to the following
equations:

H+(aq) + HCO3–(aq) H2O(l) + CO2(g)

2H+(aq) + CO32–(aq) H2O(l) + CO2(g)

Calculate the total number of moles of acid used, and thus, by using the ratio quoted in part
(ii), calculate [HCO3–(aq)] and [CO32–(aq)] in the lake.
[6]
Amount of acid used = 22.0 x 10–3 x 0.20
= 4.40 x 10–3 mol

Let x be the no of moles of HCO3–

Thus, no of moles of CO32– = 0.958 x
Based on stoichiometry of eqns, the nos of moles of acid required
= x + (2 x 0.958 x)
= 2.916 x

2.916 x = 4.40 x 10–3 mol

x = 1.51 x 10–3 mol
Concentration of HCO3– =(1.51 x 10–3 mol)/10.0 x 10–3) = 0.151 mol dm–3
Concentration of CO32– = 0.958 x 0.151 = 0.145 mol dm–3

Question 2

Piperidine is a monoacidic base and is widely used building block and chemical reagent in the
synthesis of organic compounds.

(i) The pH of an aqueous solution of piperidine is 10.1. Calculate the concentration of hydroxide
ions in the solution.

pOH = 14-10.1
= 3.9
[OH−] = 10−3.9
= 1.26 x 10−4 mol dm−3
[1]

5
(ii) In a titration, 25 cm3 of the aqueous solution of piperidine in (b)(i) was found to react completely
with 30 cm3 of 0.15 mol dm-3 of HCl (aq). Calculate the concentration of piperidine solution.

CpiperidineVpiperidine = CHCl VHCl

Cpiperidine(25/1000) = (30/1000) (0.15)
Cpiperidine = 0.180 mol dm−3

[1]

(iii) With reference to your answers to (i) and (ii), explain why piperidine is a weak base.

Concentration of OH− is much lower than piperidine concentration

Piperidine did not undergo complete dissociation to give OH−. Thus it is a
weak base.

[1]

6
2. Introduction to Organic Chemistry Functional Group: [Memorise]
an element (e.g. Br), or combination of elements
(I) Overview (e.g. OH, CO2H, NH2, NO2) responsible for
1. Formulae of Organic Compounds specific properties of an organic compounds
[Understand + Apply]
Functional Examples
ratio of number of atoms of the Classes
group Structural Displayed
Empirical
elements present in one
formula H
molecule Alkane – CH4 H C H
actual number of atoms of the H
Molecular
elements present in one H H
formula Alkene C C CH2CH2 C C
molecule H H

Structural shows how the constituent

formula atoms of a molecule are C6H6
joined together H
detail structure of molecule Arene H C H
showing the arrangement of all C6H5CH3
Full structural
or Displayed atoms and bonds
formula *Note: All the bonds between H
Halogenoalkane —X CH3Cl H C Cl
atoms must be shown H
(X = F, Cl, Br,
Stereochemical show spatial arrangement of I)
Cl

bonds, atoms and groups in Halogenoarene C6H5Cl

Formula
molecule in 3-D H
Alcohol CH3OH H C O H
E.g. Glucose —OH
H

Empirical formula: CH2O O

H
Phenol C6H5OH
Molecular formula: C6H12O6
Structural formula: HOCH2(CH(OH))4CHO Aldehyde
O
HCHO
O
C H H C H

H O H
O CH3-
Displayed formula: Ketone C COCH3
H C C C H
H H

O O
HO OH Carboxylic acid HCOOH H C
C O H
OH O H
Stereochemical formula: O O
O
HO OH Acyl chloride C Cl CH3COCl CH3 C
Cl
O
2. Classification of Organic Compounds Ester
O
HCOOCH3
H C H
C O O C H
[Memorise] H

Hydrocarbons: H H

compounds containing carbon and hydrogen only Amine CH3NH2 H C N

H H
Alkanes (CnH2n+2): NH2 H
simplest hydrocarbons containing only single bonds; Phenylamine C6H5NH2 N
H
Forms the skeleton / backbone of organic molecules
O H
Molecular Structural O
Name Amide C N HCONH2 H C N
formula formula H

CH4 CH4 methane H

C2H6 CH3CH3 ethane Nitrile C N CH3CN H C C N

H
C3H8 CH3CH2CH3 propane H H
C4H10 CH3(CH2) 2CH3 butane Ether —O— CH3OCH3 H C O C H
H H
C5H12 CH3(CH2) 3CH3 pentane
C6H14 CH3(CH2) 4CH3 hexane Homologous series:
C7H16 CH3(CH2) 5CH3 heptane family of compounds containing same functional
C8H18 CH3(CH2) 6CH3 octane group but differing by a common increment of CH2
C9H20 CH3(CH2) 7CH3 nonane between successive members
C10H22 CH3(CH2) 8CH3 decane Saturated compounds:
contain only single bonds
Alkyl groups (CnH2n+1—): Unsaturated compounds:
formed by removal of one H atom from the contain multiple bonds, e.g. C=O, CN
corresponding alkane; denoted by R Aliphatic compounds:
Molecular formula Alkyl group Name contain chains of interlinked C atoms
CH4 CH3— methyl Alicyclic compounds:
CH3CH3 CH3CH2— ethyl ring compounds containing C–C / C=C
CH3CH2CH3 CH3CH2CH2— propyl Aromatic compounds: contain benzene ring

7
 3. Hybridisation (of Carbon) Maximum number of stereoisomers = 2n
[Understand + Apply] where n = total number of cis-trans double bonds
Type of
Bond
Shape and and chiral centers
formed by Example
hybridisat n bond angle **Note:
carbon
 When drawing cis trans isomers, must
4 sigma show trigonal planar arrangement about
bonds Tetrahedral, each C in C=C bond.
sp3
(all single 109.5o
bonds)
 When drawing enantiomers, must show
wedge bonds and tetrahedral arrangement
Ethane
about chiral carbon.

3 sigma
and 1 pi
5. Reaction Types and Reaction Mechanisms
sp 2
bonds Trigonal [Understand + Apply]
Ethene
(double planar, 120o
bond Common types of reaction are:
present) 1) Free radical Substitution (alkane)
2) Electrophilic Substitution (arene)
Benzene 3) Nucleophilic Substitution (halogenoalkane)
2 sigma 4) Electrophilic Addition (alkene)
HCCH
and 2 pi 5) Nucleophilic Addition (carbonyl cpd)
o
sp bonds Linear, 180
Ethyne
(triple bond
present)
Substitution & addition respectively

4. Isomerism Substitution:
[Understand + Apply]
an atom or group of atoms replaces another
Constitutional isomerism
(same molecular formula, e.g. CH3CH2Cl + OH–  CH3CH2OH + Cl–
different structural formula)
Addition:
two molecules combine to form a single product
e.g. H2C=CH2 + Br2  CH2Br–CH2Br
Chain isomerism Position isomerism
(compounds with same molecular formula)

(differ in the way the (differ in the position of Elimination:

chain of C atoms are functional group)
linked together) involves removal of atoms or groups of atoms from
adjacent atoms to form a multiple bond
CH3 CH2 CH2 CH2 CH3 CH3 CH2 CH2 CH2 OH e.g.
Isomerism

CH3 CH CH2 CH3 CH3 CH CH2 CH3 CH3 CH CH2 + OH– CH3 CH CH2 + H2O + Br–
CH3 OH
H Br
Functional group isomerism differ in
functional group (alcohol and ether, aldehyde and
ketone, carboxylic acid and ester)
Homolytic fission:
CH3 CH2 CH2 CH2 OH CH3 CH2 CH2 CH2 CHO two shared electrons in covalent bond are split
CH3 CH2 O CH2 CH3 CH3 CH2 CO CH2 CH3 equally between atoms, giving rise to free
radicals
Stereoisomerism
(same molecular formula, same structural formula, Cl Cl Cl + Cl (half-arrow)
different spatial arrangement of atoms)
Heterolytic fission:
two shared electrons in covalent bond are split
Cis-trans isomerism Enantiomerism unequally between atoms, giving rise to an ion-
(due to restricted rotation about (2 non-superimposable mirror pair
bonds, e.g. C=C double bond) images, known as enantiomers)

H H H Br mirror plane Cl Cl Cl + Cl (full arrow)

C C C C H H
Cl Br Cl H Carbocation: ion with a +ve charge on C atom
cis trans C* *C

(identical groups (identical groups HO CH3 H3C OH Carbanion: ion with a –ve charge on C atom
on same side) on opposite side) Cl Cl
(+) (–)
H H H H
dextrorotatory laevorotatory
H H H Br (rotate clockwise) (rotate anti-clockwise)
H H H H a 1:1 molar mixture of the 2 enantiomers
is called a racemic mixture
Cl Br Cl H
2 different substituents on each 4 different substituents on a C
of the double bond C atom (chiral center)

8
Nucleophile: e.g. carboxylate anion
O O O
 Negative ions (e.g. HO–, CN–, Cl–, Br–, I–) or C C C
compounds in which an atom has an O O O
unshared pair of electrons available for
donation (e.g. NH3, H2O, RNH2, ROH) Inductive effect:
polarization (permanent displacement of
 Attacks region of +ve charge (or e poor electrical charge) due to the electron-donating or
region), withdrawing effect (relative to hydrogen) of an
e.g. C in +C=O- group atom or group of atom in a chemical bond

Electrophile:
 Positive ions (e.g. H+, H3O+, Br+, Cl+, NO2+, R+) e-donating e-withdrawing
or molecules containing an atom which can act –CnH2n+1 –X (X = F, Cl, Br, I), –OH, –OR,
as an electron-acceptor (e.g. BF3, AlCl3) (alkyl group) –NH2, –NR2, –NO2, –C(=O)
 Attacks region of ve charge (or e rich
region), e.g. C=C bond, benzene Explanation of stability of carbocations by
inductive effect:
Free radical:
species containing an unpaired electron,  Carbocation is stabilized by charge dispersal
e.g. Cl•, H3C• and it destabilized by charge intensification.

Reaction mechanisms: G donates e by electrons donating

inductive effect, +ve charge is
The stoichiometric equation for an organic
reaction does not indicate how the reaction takes dispersed and cation is stabilized.
place. The sequence of steps by which the
reaction takes place, transforming the reactants
into products, is called the reaction mechanism.
G withdraws e by electrons
**Note: QUICK TIPS TO IDENTIFY REACTION withdrawing inductive effect, +ve
MECHANISM: charge is intensified and cation is
destabilized.
1. Identify the nature of the reagent/ organic
molecule  More alkyl groups bonded to C+, +ve
2. Identify if double bond is broken (addition charge is more dispersed, more stable the
reaction), removal of any molecule carbocation.
(elimination molecule), replacement of any
atoms (substitution reaction)
< < <
6. Factors Affecting Reactivity of Organic
Compounds Primary 10 Secondary 20 Tertiary 30
[Understand + Apply]
Increasing stability
Resonance / Mesomeric effect: Steric (hindrance) :
redistribution of  electrons through the 
when large groups on a molecule ‘get in the way’
orbitals in molecules with multiple bonds, leading
and hinder the reaction
to stabilization of molecules / ions
e.g. 2,6-dimethylbenzoic acid is resistant to
e.g. benzene normal methods of esterification due to steric
canonical structures
resonance
hindrance of the 2 adjacent –CH3 groups.
H H hybrid
H C H H C H
C C C C
C C C C
H C H H C H
H H

9
(II) Exercise

Question 1

Name the functional groups present in the following compound:

Strategy: Must memorise/remember the structures of all functional groups well.
CH C(OH)CH3

NH2
COOH

Alkene, alcohol, amine, carboxylic acid

**[Alkane and arene (benzene) are not considered to be a functional group as they are part of the
backbone in C chain.]

Question 2

For each of the following compounds,

O CH3

H3C C
CH3
Compound I Compound II
Predict the hybridization and the geometry for each carbon atom.
Strategy: Deduce from the no. of sigma & pi bonds each C has
*Single bond has 1 sigma bond, double bond has 1 sigma and 1 pi bonds

For Compound I For Compound II

2
For C in C=O: sp (Trigonal planar) For C in –CH3, sp3 (Tetrahedral)

For C in –CH3, sp3 (Tetrahedral) For C in benzene ring: sp2 (Trigonal planar)

Question 3

Draw all the constitutional and cis-trans isomers which are possible for dichloropropene, C3H4Cl2.
*Strategy: Molecular formula given, hence draw all constitutional isomers first. Then identify which
structure has each C in the C=C bond which is not bonded to 2 identical groups for cis-trans isomers.
Cl C =C HC H 3
C H 2 =C C H2
Cl
Cl Cl
1,1-dichloroprop-1-ene
2,3-dichloroprop-1-ene
H C H3 Cl C H3
C =C C =C
Cl Cl H Cl Cl

cis trans C H 2 =C HC H

1,2-dichloroprop-1-ene Cl

Cl C H2C l H 3,3-dichloroprop-1-ene
C H2C l
C =C C =C
H H Cl H
cis trans
1,3-dichloroprop-1-ene
10
Question 4

Pyrethrin is a natural insecticide made from some chrysanthemum species.

O
**C=C double bond inside the
O ring does not have cis-trans
isomers due to the ring strain
O for trans configuration.

[Must know how to identify chiral carbon in the ring structure and deduce no. of stereoisomers]

Fill in the blanks:

The total number of C=C bond
1
showing cis-tans isomerism
The total number of chiral carbon 3
The total number of
21+3 = 16
stereoisomers

Question 5

Determine whether each of the following molecules exhibits enantiomerism and/or cis-trans isomerism. If
so, draw the stereoisomers.

(i) C6H5CH=C(CH3)2

The compound does not exhibit cis-trans isomerism as one of the C atoms of the C=C bond is
bonded to 2 identical –CH3 groups.
The compound does not exhibit enantiomerism as there is no chiral centre.

(ii) CH3
CH3CH2CH CHCH
Cl
Strategy: For compound which exhibits both enantiomerism and cis-tans isomerism, draw 2 pairs
of enantiomers which are cis and trans.

The compound exhibit enantiomerism as there a chiral centre bonded to 4 different groups.
The compound exhibit cis-trans isomerism as one of the C atoms of the C=C bond is not bonded
to 2 identical groups.

CH3 CH3
CH3CH2 C C CH2CH3
Cl Cl C C
C C
H H H
H H H

cis cis

CH3 CH3
H
CH2CH3
H C C
Cl Cl C C
C C CH
H H H H 2CH3
CH3CH2 H

trans trans
Mirror plane

11
Question 6

State the type of reaction for each of the following:

Reaction Type of reaction

Electrophilic addition
(a) CH2=CH2 + HI  CH3CH2I

Nucleophilic substitution
(b) CH3CH2Br + CN  CH3CH2CN + Br

(c) CH3CHBrCH3 + KOH (in ethanol)  CH2=CHCH3 + KBr Elimination

(d)
HI in CH2COOH I: Electrophilic addition
CH3CH=CHCH3 CH3CH2CHICH3
I II: Nucleophilic substitution
NaOH (aq) II

CH3CH2CH(OH)CH3

12
3. Alkanes H H
H C H H C H
(I) Overview H H H H H
H 1C 2C C C H H C C C H
3 4 1 2 3
Saturated aliphatic hydrocarbon of general H H H H H H
(NOT 4 3 2 1 ) H C H
formula CnH2n+2
H
1. Nomenclature [Understand + Apply] Step 4:
suffix –ane combine the substituent with the parent chain
- if some alkyl groups occurs more than once as
Molecular Name Structural substituents, indicate by prefix di-, tri-, tetra-,
formula formula etc;
CH4 methane CH4 - arrange substituents in alphabetical order,
C2H6 ethane CH3CH3 ignoring the prefixes such as di-, tri-
C3H8 propane CH3CH2CH3 H H
H C H H C H
C4H10 butane CH3(CH2)2CH3 H H H H H
C5H12 pentane CH3(CH2)3CH3 H 1C 2C C C H 2-methylbutane
3 4
H C C C H 2,2-dimethylpropane
1 2 3
H H H H H H
C6H14 hexane CH3(CH2)4CH3 H C H
H
C7H16 heptane CH3(CH2)5CH3
C8H18 octane CH3(CH2)6CH3 2. Physical Properties [Understand + Apply]
C9H20 nonane CH3(CH2)7CH3 Insoluble in water, but soluble in benzene, ether
C10H22 decane CH3(CH2)8CH3 (non-polar)
Constitutional (chain) isomerism exists in Floats on top of water (less dense)
alkanes containing  3 carbon atoms (due to
Viscosity of liquid alkane es with ing Mr as long
branching of chain)
H chain tangle up
H H H C H
H H H H
H C C C C H
H C
H
H
H
H H H H H
H C C C C C H
H C H
H H H
H H Melting and boiling pt:
H C C C H
H C C C H H C C C C H
H H H H
H H H
H H H H H
H H H H
H H
H C H  b.p. es with number of C atoms ( no. of e
H
butane, C4 H10
  instantaneous dipole-induced dipole
pentane, C5H12 interactions
Nomenclature of branched chain isomer  m.p. es in zig-zag manner (packing impt)
Step 1:  C1–C4 : gas; C5–C17 : liquid;  C18 : solid
identify parent chain (longest continuous carbon Reason:
chain)
H H Branched chain isomer has lower b.p. than
H C H H C H straight chain isomer, as they are more spherical,
H H H H H
H C C C C H parent : butane H C C C H parent : propane hence packed less closely with decrease in
H H H H H H dispersion force between molecules.
H C H
H Effect of branching on packing and on m.p. is
Step 2 : irregular.
identify substituents on parent chain which are
alkyl groups (general formula CnH2n+1–) 3. Cycloalkanes [Understand + Apply]
H
substituent : methyl
H substituent : methyl Saturated alicyclic hydrocarbons of general
H C H H C H formula CnH2n
H H H H H
H C C C C H parent : butane H C C C H
Molecular Structural
H H H H H H Name formula
H C H formula
substituent : methyl
H
cyclopropane C3H6 (CH2)3,
Step 3 :
cyclobutane C4H8 (CH2)4,
determine position of alkyl group(s) by numbering
the carbon atoms consecutively from one end of cyclopentane C5H10 (CH2)5,
parent chain to the other, such that a smaller digit
cyclohexane C6H12 (CH2)6,
is assigned to carbon attached to substituent
CH3
methylcyclohexane C7H14
CH3
1,2-dimethylcyclohexane C8H16
CH3

13
4. Preparation and Reactions
[Memorise + Apply]
**Free-Radical Substitution
Preparation of Alkanes
[Memorise + Apply]
 Reduction (Hydrogenation) [Mechanism for H2 only]
e.g. Stoichiometric equation:
uv
CH3CH2CH3 + Cl2  CH3CHClCH3 + HCl

Mechanism: Free radical substitution

Reagent: Hydrogen gas Initiation : Heat/light provides energy for
Condition: Ni catalyst, 140 oC, OR homolytic cleavage of Cl–Cl bond to
Pt or Pd catalyst, room temperature generate free radicals
UV
Reactions of Alkanes Cl––Cl  2Cl•
light
 Since alkane molecules are non-polar, they
are inert towards polar reagents such as Propagation: In each step, a radical is
HCl and H2O. consumed while another is
generated
 Combustion
 Reaction highly exothermic  hydrocarbons CH3CH2CH3 + Cl  CH3CHCH3 + HCl
used as fuel
 Methane (natural gas or cooking gas) burns CH3CHCH3 + Cl2  CH3CHClCH3 + Cl
with a clean blue flame tinged with a little yellow.
Termination: free radicals are consumed but
Very little ‘soot’ (carbon) is formed. Burning of
not generated
higher alkanes gives rise to sooty flames.
2Cl  Cl2
 Complete combustion of hydrocarbons
provides the basis for quantitative analysis. CH3CHCH3 + Cl  CH3CHClCH3
y y
CxHy + ( x+ ) O2 → xCO2 + ( ) 2CH3CHCH3  (CH3)2CHCH(CH3)2
4 2
H2O **Note: You must know how to describe its
reaction mechanism.
 Amount of CO2 and H2O produced can be
measured and composition of hydrocarbon can  A single free radical (once formed) can take
be calculated. part in a chain reaction sequence, giving a
large number of products
 Incomplete combustion (in limited O2) leads to  More than one hydrogen atoms in alkanes can
formation of soot (carbon), and harmful carbon be replaced by chlorine sequentially with
monoxide (CO). production of HCl.
 Reaction is not ‘clean’, giving a mixture of
 Substitution of alkanes by X2 gives
organic products
halogenoalkanes
 Monosubstitution : excess alkane
 Alkanes react with halogen to produce Polysubstitution : excess chlorine
halogenoalkanes via free radical substitution
in the presence of UV light or under high
temperature. 5. Reactivity of Halogens [Understand + Apply]
Reactivity of halogen with alkanes decreases
o
250–400
300 C C
o down Group 17: F2 > Cl2 > Br2 > I2
C H + Cl2 C Cl + HCl F2: Reaction proceeds with explosive violence,
Or UV light hence cannot be used in laboratory.
alkane mixture of Cl2 & Br2: Reaction occurs at 250–400 oC or UV
halogenoalkanes
light.
I2: Least reactive as iodine atoms do not react with
 One or more of the hydrogen atoms in the alkanes.
alkane can be substituted by the halogen
atoms. E.g. For CH4 + Cl2  CH3Cl + HCl ;
Hrxn 1 = –119 kJ mol–1 (more exothermic)
e.g. CH3CH3 + Cl2  CH2ClCH2Cl + 2HCl

14
 For CH4 + Br2  CH3Br + HBr; than the secondary (2o) or primary radical (1o) that
Hrxn 2 = –44 kJ mol–1 has fewer alkyl groups.

Reasons:
The bond energy released in the formation of
C–halogen and H–halogen bonds in the
propagation steps is getting lesser when the
size of the halogen atom increases down the
group. Hence, this leads to  ease of
substitution since Hrxn becomes less
exothermic down the group.

6. Rate of Substitution at 1o, 2o & 3o Carbon

Atoms [Understand + Apply]
e.g. When butane undergoes monochlorination,
there are two possibilities for the substitution to
take place as shown below.
H H H H H H H H
Cl2
H C C C C H C C C C Cl Cl
Cl
H H H H H H H H
H H H H 1-chlorobutane
1o alkyl radical expected = 60%
H C C C C H
H H H H yield = 30%
H H H H H Cl H
Cl Cl2 H C C C C H
H C C C C H Cl
H H H H H H H H
2-chlorobutane
2o alkyl radical
expected = 40%
yield = 70%

How to determine the expected ratio of

1-chlorobutane and 2-chlorobutane produced?
 Based on probability factor, H atoms at any
6 positions around primary (1o) C atoms
and any 4 positions around secondary (2o)
C atoms in butane can be substituted by Cl
atom.
 Hence, the expected ratio of the of
1–chlorobutane to 2–chlorobutane formed
is 60% : 40%.

However, 2-chlorobutane is the major product

(yield = 70%) in the above substitution reaction.

Why is there is a discrepancy between the

expected ratio and the ratio of the
monochlorinated products obtained
experimentally?
Reasons:

 Stability of radicals: 3º > 2º > 1º > •CH3

Alkyl groups, R, exert electron donating

inductive effect and they can stabilise a carbon
radical by increasing the electron density on
the electron deficient carbon atom carrying the
odd electron. The more alkyl groups bonded to
this carbon, the more stable the radical. This
explains why the tertiary(3o) radical is more stable

15
(II) Exercise

Question 1

Tetrachloromethane, CCl4, is one type of chlorine containing organic compound. It can be produced
from methane.

(i) Name the type of mechanism to produce tetrachloromethane, CCl4. State the reagent(s) and
conditions for this reaction. [2]

Hint: Must memorise all the reaction name (name of mechanism), reagents and conditions
for every Alkanes reaction.

Name of mechanism: Free radical substitution

Reagent: Excess Cl2(g) [Excess chlorine for full substitution]
Condition: uv light

(ii) Describe the reaction mechanism to form the intermediate CH2Cl2. [5]

Hint: Must memorise all the descriptions and equations for Free Radical Sub for Alkanes.

Hint: Disubstitution  Each H atom in CH2Cl2 will be substituted by Cl step by step  4

propagation steps

Name of mechanism: Free radical substitution

Initiation: High temperature/UV light provides energy for homolytic cleavage of Cl–Cl
bond to generate free Cl• radicals.

UV
Cl––Cl  2Cl•
light

Propagation: A Cl radical is consumed in one step and another Cl radical is generated
in the other step to keep the chain reaction going.

(1) Cl● + CH4  ●CH3 + HCl

(2) ●CH3 + Cl2  CH3Cl + Cl●

(3) Cl● + CH3Cl  ●CH2Cl + HCl

(4) ●CH2Cl + Cl2  CH2Cl2 + Cl●

Termination: Free radicals are consumed but not generated. This terminates the reaction
since radicals are consumed.

Cl● + Cl●  Cl2

Cl● + ●CH3  CH3Cl

●CH2Cl + ●CH3  CH3CH2Cl etc

16
 4. Alkenes

(I) Overview

Unsaturated aliphatic hydrocarbon containing a C=C double bond with general formula CnH2n
(n  2)
Constitutional isomerism and stereoisomerism exists in alkenes containing  3 carbon atoms
e.g. C4H8
 Chain isomerism: (due to different arrangement of C atoms)
H H H CH3
C C C C
H CH2 CH3 H CH3
 Position isomerism: (due to different position of double bond)
H1 2 H H2 3 H
C C3 4 1 C C4
H CH2 CH3 H3 C CH3
 Cis-trans isomerism: (due to restricted rotation about C=C)
H H H3C H
C C C C
H3C CH3 H CH3
cis trans
So C4H8 has in total 4 isomers.

1. Nomenclature [Memorise + Apply]

suffix –ene
Molecular formula Name Structural formula
C2H4 ethene CH2=CH2
C3H6 propene CH2=CHCH3
C4H8 butene CH2=CHCH2CH3
C5H10 pentene CH2=CH(CH2) 2CH3
C6H12 hexene CH2=CH(CH2) 3CH3

Step 1 : identify parent chain (longest continuous carbon chain which contain C=C)

H CH3 H3C CH2 CH2 CH3

C C parent : butene C C parent : hexene
H CH2 CH3 H CH2 CH3
Step 2 : determine position of C=C by numbering the carbon atoms consecutively from one end of
parent chain to the other, such that lower numbers are assigned for the two C=C carbons;
position of double bond is indicated by the smaller of the two numbers, immediately before
the suffix –ene
1 4 5 6
H 1 2 CH3 H3C CH2 CH2 CH3
C C 3 4 parent : but-1-ene 2 C C 3 parent : hex-2-ene
H CH2 CH3 H CH2 CH3

Step 3 : identify substituents on parent chain which are alkyl groups (general formula –CnH2n+1);
indicate position of alkyl groups based on numbering in step 2
1 4 5 6
H 1 2 CH3 substituent : methyl H3C CH2 CH2 CH3
C C 3 4 parent : but-1-ene 2 C C3 parent : hex-2-ene
H CH2 CH3 H CH2 CH3 substituent : ethyl

2-methylbut-1-ene 3-ethylhex-2-ene

17
 2. Physical Properties [Understand + Apply]
 Insoluble in water, but soluble in benzene, ether (non-polar)
 Floats on top of water (less dense)
 B.p. es with carbon number due to  instantaneous dipole-induced dipole interactions
between molecules with larger electrons number; branching es b.p.; cis-isomer has larger
dipole moment than trans-isomer (= 0 if same groups on each of the double bond C)
C1–C4: gas;  C5: liquid and solid

3. Preparation and Reactions

 Preparation of Alkenes [Memorise + Apply]

Reagents & Example of balanced

Reaction Remarks
conditions equations
Excess conc. H2SO4,
From alcohols 170 oC OR CH3CH2CH2OH
-
(Elimination)  CH3CH=CH2 + H2O
Al2O3, 300 – 350 oC
From CH3CH2CH2Br + The major product
NaOH or KOH in
halogenoalkanes KOH(ethanol) formed is the more stable
ethanol, heat
(Elimination)  CH3CH=CH2 + KBr + H2O / substituted alkene.

 Reactions of Alkenes [Memorise + Apply, esp. electrophilic addition and oxidative cleavage]
Type of Reagents & Examples of balanced
Remarks
reaction conditions equations
Reactivity : HI > HBr > HCl (in order of
decreasing acid strength)
Follow Markonikov’s rule: H of HBr is
attached to carbon atom of C=C bond
with more H atoms bonded to it.
*Reason: Electrophile adds so as to
form a more stable carbocation
preferentially.
Stability of carbocation:
R' R' H
CH3CH=CH2 + HBr R C R'' > R C H > R C H
HBr, room temp.  CH3CH(Br)CH3
3o 2o 1o
Electrophilic
addition Tertiary (3o) carbocation is the most
stable as it has 3 electron donating
alkyl (R) groups, which exert electron
donating inductive effect to help
disperse the positive charge on
carbocation more than that of the
secondary (2o) and primary (1o)
carbocations.
You must know how to describe its
reaction mechanism. (see reaction
mechanism)
Observation: Decolourisation of
reddish-brown bromine in CCl4.
Br2 in CCl4, CH3CH=CH2 + Br2
room temp.  CH3CH(Br)CH2(Br) You must know how to describe its
reaction mechanism. (see reaction
mechanism)

18
 Type of Reagents & Examples of balanced
Remarks
reaction conditions equations
Reactivity: F2 > Cl2 > Br2 > I2
F2 reacts explosively. Reaction with
I 2 is very slow and incomplete.

Observation: Decolourisation of
CH3CH=CH2 + Br2 + H2O orange aqueous bromine.
Br2(aq), room temp.  CH3CH(OH)CH2Br
Follow Markonikov’s rule: Br is
+ HBr attached to carbon atom of C=C bond
with more H atoms bonded to it.
Electrophilic
addition You must know how to describe its
reaction mechanism. (see reaction
mechanism)
Conc. H2SO4,
followed by water,
warm
Follow Markonikov’s rule: H of H2O is
CH3CH=CH2 + H2O attached to carbon atom of C=C bond
(For industrial  CH3CH(OH)CH3 with more H atoms bonded to it.
production of
alcohol: steam,
300oC, 65 atm,
H3PO4 catalyst)
H2, Pt or Pd
catalyst, room
temp. CH3CH=CH2 + H2
Reduction -
 CH3CH2CH3
OR H2, Ni catalyst,
140 oC

CH3CH=CH2 + 9/2O2 Incomplete combustion (in limited O2)

O2 (combustn) leads to formation of soot (carbon), and
 3CO2 + 3H2O harmful carbon monoxide (CO).
Oxidation
CH3CH=CH2 + [O] + H2O Observation: Purple colour of KMnO4
OH–/KMnO4,
 CH3CH(OH)CH2(OH) decolourised with simultaneous
cold/room temp.
(diol) precipitation of brown MnO2.

CH3CH=CH2 + 5[O] Observation: Purple colour of KMnO4

decolourised.
 CH3CO2H + CO2
+ H2O In general,
Oxidative CHR=CR2 + 3[O]
cleavage H+/KMnO4,heat **Note: You must know  RCO2H (carboxylic acid)
how to write oxidation + R2CO (ketone)
equation for the
alkenes by using [O] CHR=CH2 (terminal alkene) + 5[O]
notation.  RCO2H + CO2 + H2O

19
 4. Mechanism [Memorise + Apply]

1. For addition of hydrogen halides 2. For addition of halogens in CCl4

e.g. CH2=CH2 + HX  CH3CHX e.g. CH2=CH2 + Br2  CH2(Br)CH2(Br)
Name of mechanism: Electrophilic addition Name of mechanism: Electrophilic addition

Step 1: Formation of carbocation by electrophilic Step 1: The electron cloud of pi () bond in ethene
attack of H+ from the polar H+–X– molecule on the polarises an approaching Br2 molecule. The
C=C bond. positive end of the polarised bromine molecule
H H H H attacks ethene.
 
C C H X H C C H + X H H
H H
H H
H C C H C C H + Br
–
Step 2: Attack by X on carbocation. H H Br

H H H H Br
H C C H + X X-
: H C C H Br

H H X
Step 2: Attack by Br– on carbocation.
H H H H
**Note: -
H C C H + Br:Br H C C H
Follow Markonikov’s rule where H of HX is
attached to carbon atom of C=C bond with more H Br Br Br
atoms bonded to it in step 1. **Note:
 Follow Markonikov’s rule where Br is attached
to carbon atom of C=C bond with more H atoms
bonded to it in step 1.
 If the reaction is done in the presence of other
anions, such as Cl– or NO3–, these anions also
attack the carbocation in step 2. Products of the
reaction will also include CH2BrCH2Cl and
CH2BrCH2NO3.
3. For addition of halogens in water
e.g. CH2=CH2 + H2O  CH2(Br)CH2(OH)
Name of mechanism: Electrophilic addition
H H H H
H C C CH3 + Br2 H C C CH3
Br
H2O Br
H H H H H H
H+
H C C CH3 H C C CH3 H C C CH3
Br OH Br OH2 Br Br
1-bromopropan-2-ol
(major product due to
higher H2O concentration)
**Note:
Follow Markonikov’s rule: Br is attached to carbon atom of C=C bond with more H atoms bonded to it in
step 1.

5. Tests for Alkenes

The following tests could be used to indicate the presence of C=C bond in alkenes.
 Decolourisation of a solution of reddish–brown Br2 in CCl4 or orange Br2 in H2O.

20
(II) Exercise

Question 1

Consider the molecule shown below.

CH2CH3

CH3 C
CH2
Give the structural formulae of the major product formed when the above molecule reacts with:

Strategy: Must know how to deduce the major products from all reactions involving Alkenes.

(i) Br2(aq) (ii) HBr under room (iii) hot acidic KMnO4
temperature
O
CH2CH3 CH2CH3
CH2CH3
Br Br CO2H
OH OH CH3 C
CH3 C H
CH3 C Br O
CH3
CH2Br + CO2 + H2O

Question 2

Shown below is a reaction scheme for converting 2-chloro-3-methylbutane into 2-chloro-2-

methylbutane:
Cl
CH3 CH CH CH3 I II
X CH3 CH2 C CH3
Cl CH3
CH3
Strategy: A change in the position of Cl indicates that the starting compound must undergo
elimination of HCl molecule to form an alkene in step I.

(i) Suggest a possible structure for compound X above.

[1]

CH3CH C CH3
CH3
(ii) Hence, give the reagents and conditions needed for steps I and II.
[2]
Step I : alcoholic KOH or NaOH, heat
Step II: HCl, room temperature

21
Question 3
An alkene, Y, has the molecular formula C8H14. One mole of Y reacts exactly with 2 moles of bromine.
Oxidation of one mole of Y by hot acidic potassium manganate(VII) yields the following organic
products, one mole of (CH3)2CO and one mole of CH3COCH2CO2H.
Strategy: From the oxidative cleavage products of alkene, identify RCO2H is from RCH=,
RCOR’ is from CRR’=, CO2 is from CH2=.

(i) Draw the structural formula of Y.

[1]
Hint: 7 C in the oxidation organic products, 1 C must be present in CO2, from the oxidative
cleavage of CH2= group in Y.

(ii) Suggest what colour change might be observed for the above reaction.
[1]
Purple colour of KMnO4 discharged/decolourised.

(iii) Using the [O] notation for the oxidation of organic compound, write a balanced equation for the
above oxidation reaction.
[1]
(CH3)2C=CHCH2C(CH3)=CH2 + 7[O]  (CH3)2CO + CH3COCH2CO2H + CO2 + H2O

Question 4
Describe, with the aid of curved arrows, the mechanism for the reaction between but-1-ene and
bromine at room temperature.
[4]
Hint: Must memorise the descriptions and equations for every step in mechanism.

22
Step 1: Formation of carbocation.
The electron cloud of pi () bond in ethene polarises an approaching Br2 molecule. The
positive end of the polarised bromine molecule which acts as an electrophile attacks ethene.
H H
C C H H
H CH2CH3
Br + H C C CH2CH3 + Br-
+
Br  Br
The secondary carbocation, rather than the primary carbocation, is formed as it is more
stable.
Step 2: Attack by Br– on carbocation.
H H H H

C --
H C
+
:
CH2CH3 + BrBr H C C CH2CH3

Br Br Br

23
Part B: Answering Skills for Integrated Questions

Question 1 (Alkenes / Isomerism / Acid-Base Equilibria)

The question is about the Chemistry of some organic compounds.

(a) An alkene, X, has the molecular formula C7H13Cl. On oxidation with hot acidified potassium
manganate(VII) solution, X gives rise to two organic compounds B and C. Compound B has a
structural formula of CH3COCH(Cl)CH2CH3.

(i) Deduce the structure of X and C. Hence, using [O] notation, write the equation for the
above reaction. [2]

The structure of C is CH3COOH.

The structure of X is CH3CH=C(CH3)CH(Cl)CH2CH3.
The equation for the above reaction is
CH3CH=C(CH3)CH(Cl)CH2CH3 + 3 [O]  CH3COOH + CH3COCH(Cl)CH2CH3

(ii) State the type of isomerism that B exhibits and draw the isomers. [2]

Enantiomerism
H H

C C
Cl
Cl CH2CH3 H3CH2C
COCH3 H3COC

Mirror plane
(iii) Write down the equation showing the major product, for the following reactions when
alkene X reacts with

I. HBr at room temperature [1]

CH3CH=C(CH3)CH(Cl)CH2CH3 + HBr  CH3CH2C(Br)(CH3)CH(Cl)CH2CH3

[H+ from HBr is added to C in C=C bond which has more H atoms bonded to it]
II. Aqueous bromine at room temperature [1]

CH3CH=C(CH3)CH(Cl)CH2CH3 + Br2 + H2O

 CH3CH(Br)C(OH)(CH3)CH(Cl)CH2CH3 + HBr
[Br+ from Br2(aq) is added to C in C=C bond which has more H atoms bonded
to it]

(iv) Name the type of reaction involved in the two reactions in (a)(iii). [1]
Electrophilic addition

(v) Compare and contrast the difference in the solubility of compounds B and C in terms of
their structure and bonding. [3]
Although compounds B and C have simple molecular structures, compound C is
soluble in water while compound B does not.
Compound C has a short hydrophobic hydrocarbon chain while compound B has
a long hydrophobic hydrocarbon chain.
Furthermore, compound C has –COOH group and it can form hydrogen bonding
with water.

24
(b) Ethanoic acid, CH3COOH is a weak organic acid.

(i) Describe qualitatively how the pH of ethanoic acid would be affected by the addition of
solid sodium ethanoate, CH3COONa, to it. [2]

Strategy: How is dissociation of CH3COOH affected by the addition of CH3COONa?

CH3COOH + H2O ⇌ CH3COO + H3O+

CH3COONa+ (a strong electrolyte) undergoes complete dissociation and

[CH3COO] in the solution is thus increased.

By Le Chatelier’s Principle, the eqm position of the above reaction will shift to the
left to remove the additional CH3COO ions added.

Hence the [H3O+] would decrease and the pH of the solution will increase.

(ii) It is found that the pH of a mixture containing 0.100 mol of ethanoic acid and 0.100 mol
of CH3COONa does not change appreciably when small amounts of strong acid or strong
alkali are added. Explain why this is so, with the help of equations. [2]

Strategy: The mixture of weak acid (CH3COOH) and salt (CH3COO—Na+) containing
conjugate base of weak acid (CH3COO—) makes up a buffer which maintains a fairly
constant pH when small amount of acid/base is added to it.

Large reservoir of salt, CH3COONa+, supplies sufficient CH3COO ions which helps
to remove added H+ (from acid added).

CH3COO + H+  CH3COOH

Large reservoir of weak acid, CH3COOH, helps to remove added OH (from alkali
added) sufficiently.

CH3COOH + OH  CH3COO + H2O

(iii) To an ethanoic acid solution of pH 5, sufficient amount of an iron (III) salt was added such
that the concentration of Fe3+ ions was 0.0100 moldm-3.

Calculate the concentration of OH ion in the ethanoic acid. Given that the ionic product
of water at 298 K is 1.00 x 10-14 mol2dm-6. [2]

At 298 K, pOH = pKw – pH = 14 – 5 =9

[OH] = 10-pOH = 1.00 x 10-9 mol dm-3

25
 (c) Another organic compound, Spironolactone is an anti-androgen used as a common component
in hormone therapy.
O

* O
*
* *
* *
O *
O

Spironolactone

Copy the structure shown above, label all the chiral centres with *. [2]
[Total: 20]

Question 2 (Gas / Energetics / Chem Eqm / Intro to Organic Chem)

Methane, being one type of organic compound which is commonly used as cooking gas in household,
is also widely used in industrial applications.

(a) In the industry, methane is used to produce methanol in a two-step process.

Step 1: CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g) ; ∆H1
Step 2: CO(g) + 2H2(g) ⇌ CH3OH(g) ; ∆H2

(i) For Step 1 reaction, initially, 3 mol of methane and 2 mol of steam were allowed to react
in a sealed vessel. At equilibrium, 5.67 mol of hydrogen gas was formed and the total
pressure was 30 atm. Calculate the value of Kp, stating its units. [3]

CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)

Initial no. of moles 3 2 0 0
Change 5.67/3 5.67/3 +5.67/3 +5.67
Eqm no. of moles 1.11 0.11 1.89 5.67

Total no. of moles of gases at eqm = 1.11 + 0.11 + 1.89 + 5.67

= 8.78 mol
PH2 = (5.67 / 8.78) x 30
= 19.4 atm

PCO = (1.89 / 8.78) x 30

= 6.46 atm

PCH4 = (1.11 / 8.78) x 30

= 3.79 atm

PH2O = (0.11 / 8.78) x 30

= 0.376 atm

Kp = (PH23 x PCO) / (PCH4 x PH2O)

= 33.1 x 103 atm2

26
(ii) When 0.100 g of the methane used in Step 1 is transferred to a 2.50 dm3 vessel at a
pressure of 95.5 Pa at 27oC, calculate the change in mass of methane gas in the vessel
if this gas were an ideal gas? [2]

Ideal gas eqn, pV= nRT = (m/Mr)RT

m = (pVMr)/RT
= (95.5 x 2.50 x10-3 x 16) / (8.31 x 300)
= 1.53 x 10-3 g

Change in mass of methane = 0.100 – 1.53 x 10-3

= 0.098 g

(iii) Use the following data, construct an energy cycle to calculate the enthalpy change for
Step 1, ∆H1. [4]

Enthalpy change of combustion of CH4(g) = 808 kJ mol-1

Enthalpy change of combustion of CO(g) = 283 kJ mol-1
Enthalpy change of combustion of H2(g) = 245 kJ mol-1
Enthalpy change of combustion of CH3OH(g) = 671 kJ mol-1
Enthalpy change of vapourisation of H2O(l) = +50.8 kJ mol-1
∆H1
2O2(g) + CH4(g) + H2O(g)  CO(g) + 3H2(g) + 2O2(g)

∆Hc(CH4)= 808

CO2(g) + 2H2O(l) + H2O(g) ∆Hc(CO) + 3 x ∆Hc(H2)

= 283 + 3(245)
∆Hvap(H2O)
= 50.8
CO2(g) + 2H2O(l) + H2O(l)

By Hess’s Law, ∆H1 – 283 + 3(–245) = –808 –50.8

∆H1 = +159.2 kJ mol-1

(iv) Explain how the yield of products in Step 1 is affected by the following changes.
[4]
I. The volume of the sealed vessel is halved at 27oC.

For Step 1: CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)

When the volume of the gas mixture is halved at constant temperature, the total
pressure of the mixture is increased. By Le Chatelier’s Principle, the system will
try to lower the pressure by forming less gaseous particles.
Thus, the position of equilibrium shifts to the left in Step 1.

II. The temperature of the equilibrium mixture is raised above 270C.

For Step 1: CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g); ∆H1 = +159.2 kJ mol-1

When the temperature of equilibrium mixture is raised above 27oC, by Le

Chatelier’s Principle, the system will try to lower the temperature by favouring
endothermic reaction.
Thus, the position of equilibrium shifts to the right in Step 1.

27
(b) The other organic compound S was used in the following synthesis route.

HCN, OH
NaCN cat.
COCH CH2 C CH CH2
III
CN
S
H2, Pt Br2(aq)
I IV

OH OH
CHCH2CH3 C CH CH2Br
OH CN
conc. HNO3, U
conc. H2SO4
II
NO2

CHCH2CH3
OH

(i) What are the respective numbers of sp, sp2 and sp3 hybridised carbon atoms in compound
U? [3]

sp: 1 sp2: 6 sp3: 3

(ii) Give the types of reaction in I to IV. [4]

I: reduction / electrophilic addition

II: electrophilic substitution
III: nucleophilic addition
IV: electrophilic addition

[Total: 20]

~ THE END ~

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