Atomic Structure

I. Atomic structure
A. Different model of atomic structure
B. Isotopic mass and relative atomic mass
1. Mass spectrometer
a) Determination of atomic mass
b) Determination of molecular mass
C. Radioactivity of nuclide
1. Nature of radioactivity
a) Penetrating power of radiation
2. Radioactive decay
a) Half life
b) Use of radioactive isotope
II. Electronic structure of atoms
A. Emission spectrum of hydrogen
1. Origin of emission and absorption spectrum
2. Pattern of energy levels of hydrogen
3. Determination of the ionization energy
a) Through the convergence limit of Lyman series
b) Through Rydberg constant
B. Detail electronic configuration
1. Definition of ionization energy
2. Successive ionization energy
3. Periodicity of First ionization energy
a) First I.E. across periods
b) First I.E. down a group
4. Quantum numbers
a) Energy of electrons in different orbitals
5. Building up of electrons in an atom
a) Aufbau principle
b) Pauli exclusion principle
c) Hund's rule
d) Building up of electrons
e) Detail electronic configuration of some atoms
6. Electronic configuration of first 36 elements
a) Extra stability of half-filled and full-filled subshell
7. Position of s-, p-, d- and f-block elements
III. Atomic orbitals
A. Shape of s, p and d orbitals
IV. Periodic Table
A. Variation in atomic radius
B. Variation in electronegativity


Energetics

I. Enthalpy Change (∆H)
A. Definition of a system
B. Definition of enthalpy (H) and enthalpy change (∆H)
1. Constant pressure process
a) Work done by a system
C. Standard enthalpy change of formation (∆H
f
o)
1. Definition of ∆H
f
o
a) Standard enthalpy change (∆Ho)
b) Standard enthalpy change of formation (∆H
f
o)
c) Standard enthalpy change of formation of an element
2. Direct determination of ∆H
f
o
a) Use of simple calorimeter
D. Other enthalpy change (∆H)
1. Examples of enthalpy change
a) Enthalpy of combustion
b) Enthalpy of atomization
c) Enthalpy of neutralization
d) Enthalpy of hydrogenation
e) Enthalpy of solution
f) Enthalpy of reaction
E. Hess’s Law
1. Indirect determination of ∆H
f
o
a) Hess’s Law
(1) Use of energy level diagram / energy cycle
(2) Use of equation
II. Bonding Energy
A. Bond energy
1. Definition of bond energy
2. Determination of bond energy term (bond enthalpy)
B. Strenght of covalent bond
1. Relationship between bond length and bond energy
2. Factors affecting the bond strength
C. Estimation of enthalpy change by bond energy
III. Energetics of formation of ionic compounds
A. Electron affinity
B. Lattice energy
1. Born-Haber cycle
a) Determination of lattice energy by Born-Haber cycle
2. Factors affecting the value of lattice energy
C. Stoichiometry of ionic compounds
IV. Gibbs free energy change (∆G)
A. Limitation of enthalpy change (∆H)
B. Entropy (S) and entropy change (∆S)
C. Gibbs free energy change (∆G)
Chemical Bonding Page 1
Chemical Bonding

I. Shape of molecule
A. Lewis structure of molecule
1. Oxidation no. of individual atoms in a molecule
2. Formal charge of individual atoms in a molecule
3. Limitation of octet rule
B. Valence Shell Electron Pair Repulsion Theory (VSEPRT)
1. Octet expansion of elements in Period 3
2. Position of lone pair
3. 3-dimensional representation of molecular shape
C. Hybridization Theory
1. Overlapping of atomic orbital
2. Hybridization theory
3. Examples
a) sp hybridizaion
b) sp
2
hybridizaion
c) sp
3
hybridizaion
d) sp
3
d hybridizaion
e) sp
3
d
2
hybridizaion
4. Structure and shape of hydrocarbons
a) Characteristic of Carbon-Carbon bond
b) Shape of hydrocarbons
(1) Saturated hydrocarbons
(2) Unsaturated hydrocarbons
(3) Aromatic hydrocarbons
(a) Delocalization of π-electrons
(b) Stability of benzene
D. Molecular Orbital Theory
II. Ionic bonding
A. Strength of ionic bond - lattice energy
B. X-ray diffraction
1. Electron density map of sodium chloride
C. Periodicity of ionic radius
1. Definition of radius
2. Periodicity of ionic radius
3. Size of isoelectronic particles
Chemical Bonding Page 2
III. Covalent bonding
A. H
2
+
ion
B. Electron diffraction
C. Covalent radius
1. Definition of covalent radius
2. Addivity of covalent radius
3. Breaking down of addivity in covalent radius and bond energy
a) Resonance
(1) Resonance structure of benzene
(2) Resonance structure of nitrate ion
(3) Rules in writing resonance structures
b) Breaking down of addivity in bond enthalpies
(1) Delocalization energy
D. Dative covalent bond
1. Examples of H
3
N→BF
3
and Al
2
Cl
6

a) H
3
N→BF
3

b) Al
2
Cl
6

IV. Bonding intermediate between ionic and covalent
A. Differences between ionic bond and covalent bond
B. Incomplete electron transfer in ionic compound
1. Electron density map of LiF comparing with those of NaCl and H
2

2. Difference among lattice energies of Na, Ag and Zn compounds
a) Lattice energies of sodium halide, silver halide and zinc sulphate
b) Bonding intermediate between covalent and ionic
3. Polarization of ionic bond
a) Fajans’ Rules in polarization of ionic bond
C. Electronegativity
1. Definition of electronegativity
2. Pauling scale of electronegativity
D. Polarity in covalent bond
1. Deflection of a liquid jet by an electric field
2. Dipole moment
a) Vector quantity of dipole moment
b) Polarity of molecule
c) Factors affecting dipole moment
(1) Inductive effect (I)
(2) Mesomeric effect / resonance effect (R)
(3) Presence of lone pair

V. Metallic bonding
A. Electron sea model of metal
B. Strength of metallic bond
C. Melting and boiling of metal
D. Strength of ionic bond, covalent bond and metallic bond
Intermolecular forces
Intermolecular Forces

I. Van der Waals’ forces
A. Discovery of van der Waals' forces
B. Origin of van der Waals' forces
1. Induced dipole-induced dipole attractions
2. Dipole-dipole interactions
3. Dipole-induced dipole attractions
C. Relative strength of different origins of van der Waals' forces
II. Hydrogen bond
A. Nature
B. Strength
C. Solubility and hydrogen bond
D. Intramolecular hydrogen bond
E. Examples of hydrogen bonding
1. Ethanoic acid dimer
2. Simple hydrides - CH
4
, NH
3
, H
2
O and HF
3. Structure and physical properties of ice
4. Biochemical importance of hydrogen bond
a) DNA
b) Protein
F. Strength of van der Waals' forces and hydrogen bond
III. Relationship between structures and properties

States of Matter

I. Solid state
A. Metallic structure
1. Hexagonal close packing
2. Cubic close packing - face centred cubic
3. Tetrahedral holes and octahedral holes
4. Body-centred cubic structure
B. Giant ionic structure
C. Covalent giant structure
1. Allotrope of carbon
a) Diamond
b) Graphite
2. Silicon(IV) oxide
D. Molecular crystal
1. Iodine – face centred cubic
2. Carbon dioxide (Dry ice) – face centred cubic

II. Gaseous state
A. Gas laws
1. Charles' law
2. Boyle's law
3. Avogadro's law
4. PVT surface
B. Ideal gas equation (Ideal gas law)
1. Molar volume
C. Determination of molecular mass
1. Experimental determination of molar mass of a gas
2. Experimental determination of molar mass of a volatile liquid
D. Dalton's law of partial pressure
1. Mole fraction
2. Relationship between partial pressure and mole fraction
Chemical Kinetics Page 1
Chemical Kinetics

I. Rates of chemical reactions
A. Definition of rate of reaction
1. Unit of rate of reaction
B. Measuring the rate of reaction
1. Different approaches
a) Constant amount approach
b) Constant time approach
2. Interpretation of physical measurements made in following a reaction
a) Volume of gas formed
b) Colorimetric measurement
II. Order of reaction
A. Rate Law or rate equation
1. Differential form and integrated form of rate law
2. Graphical presentation of reaction rate
3. Order of reaction
a) Experimental determination of order of reaction
(1) By measuring the rates of reaction at different reactant concentration
(2) By plotting graph of ln rate versus ln [X]
B. Examples of different reaction
1. First order reaction
a) Half life (t
½
)
b) Carbon-14 dating
c) Examples of calculation
2. Second order reaction
3. Zeroth order reaction
III. Collision theory and activation energy
A. Collision theory
1. Distribution of molecular speed (Maxwell-Boltzman distribution)
2. Effect of temperature change on molecular speeds
3. Collision theory and activation energy
a) Arrhenius equation
B. Determination of activation energy
1. By measuring the rate of reaction at different temperature
2. By plotting graph of ln k versus
1
T

3. By plotting graph of ln rate versus
1
T

Chemical Kinetics Page 2
IV. Energy profile of reaction
A. Transition state
1. Order of reaction leads to interpretation of reaction mechanism at molecular
level
a) Multi-stages reaction
(1) Alkaline hydrolysis of 2-chloro-2-methylpropane
(2) Reaction between bromide and bromate(V) in acidic medium
b) Rate determining step
2. Energetic stability and kinetic stability
B. Effect of catalyst
1. Characteristics of catalyst
2. Theory of catalyst
a) Homogeneous catalysis
b) Heterogeneous catalysis
3. Application of catalyst
a) Use of catalyst in Haber process and hydrogenation
b) Catalytic converter
c) Enzymes
V. Factors influencing the rate of reaction
A. Concentration
B. Temperature
C. Pressure
D. Surface area
E. Catalyst
F. Light
Chemical Equilibria Page 1
Chemical Equilibria

I. Nature of equilibrium
A. Dynamic nature
B. Examples of equilibrium
1. Bromine water in acidic and alkaline medium
2. Potassium dichromate in acidic and alkaline medium
3. Hydrolysis of bismuth chloride
C. Equilibrium law
1. Introduction to different equilibrium constant (K) – K
c
, K
p
, K
w
, K
a
, K
b
, K
In
, K
d

2. Equilibrium constant (K
c
and K
p
)
3. Degree of dissociation (α)
4. Concentration of solid
5. Determination of equilibrium constant (K
c
)
a) Esterification
b) Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

6. Relationship between rate constant and equilibrium constant
D. Effect of change in concentration, pressure and temperature on equilibria (Le
Chaterlier's principle)
1. Concentration
2. Pressure
3. Temperature
a) Equation : ln K = constant -
∆H
T

4. Effect of catalyst on equilibria
5. Examples of calculation

Chemical Equilibria Page 2
II. Acid-base Equilibria
A. Acid-base Theory
1. Arrhenius definition
2. Bronsted-Lowry definition
3. Lewis definition
B. Strength of acid
1. Leveling effect
C. Dissociation of water
1. Ionic product of water
D. pH and its measurement
1. Definition of pH
2. Temperature dependence of pH
3. Measurement of pH
a) Use of pH meter
(1) Calibration of pH meter
b) Use of indicator
(1) Colour of indicator
E. Strong and weak acids/bases
1. Measuring of pH or conductivity of acid / base
2. Dissociation constant (K
a
and K
b
)
a) Dissociation of polybasic acid
(1) Charge effect
3. Calculation involving pH, K
a
and K
b

a) Relationship between K
a
and K
b
(pK
a
and pK
b
)
b) Relationship between pH, pOH and pK
w

c) Some basic assumptions applied
4. Experimental determination of K
a

F. Buffer
1. Principle of buffer action
a) pH of an acidic buffer
b) pH of an alkaline buffer
2. Calculation of buffer solution
G. Theory of Indicator
H. Acid-base titration
1. Difference between equivalence point and end point
2. Titration using pH meter
3. Titration using indicator
a) Choosing of indicator
4. Thermometric titration
5. Conductimetric titration
a) Strong acid vs Strong base
b) Weak acid vs Strong base
c) Weak acid vs Weak base

Chemical Equilibria Page 3
III. Redox Equilibria
A. Redox reaction
1. Balancing of redox reaction
a) By combining balanced half-ionic equation
(1) Steps of writing balanced half-ionic equation
(2) Combining half-ionic equations
b) By the change in oxidation no.
2. Faraday and mole
3. Calculation of mass liberated in electrolysis
B. Electrochemical cells
1. Measurement of e.m.f.
a) Potentiometer
b) High impedance voltmeter / Digital multimeter
2. Use of salt bridge
a) Requirement of a salt bridge
b) An electrochemical cell does not need salt bridge
3. Cell diagrams (IUPAC conventions)
C. Electrode potentials
1. Standard hydrogen electrode
2. Relative electrode potential (Standard reduction potential)
a) Meaning of sign and value
3. Electrochemical series
4. Use of electrode potential
a) Comparing the oxidizing and reducing power
b) Calculation of e.m.f. of a cell
c) Prediction of the feasibility of redox reaction
(1) Disproportionation reaction
D. Secondary cell and fuel cell
1. Lead-acid accumulator
2. Hydrogen-oxygen fuel cell
E. Corrosion of iron and its prevention
1. Electrochemical process of rusting
2. Prevention of rusting
a) Coating
b) Sacrificial protection
c) Alloying


Phase Equilibria


I. One component system
A. Water
1. Phase diagram of water
2. Isotherm of water
3. PVT surface of water
B. Carbon dioxide
1. Phase diagram of carbon dioxide
2. Isotherm of carbon dioxide
II. Two components system
A. Ideal system
1. Raoult's law
2. Composition of the liquid mixture comparing with composition of the vapour
3. Boiling point-composition diagram
a) Definition of boiling point
b) Boiling point-composition diagram
c) Fractional distillation
B. Non-ideal solution
1. Deviation from Raoult's law
a) Positive deviation
b) Negative deviation
c) Enthalpy change of mixing
2. Elevation of boiling point and depression of freezing point by an involatile solute
3. Boiling point of two immiscible liquid
a) Steam distillation

III. Three components system
A. Partition of a solute between two phases
1. Solvent extraction
a) Calculation
2. Paper chromatography
a) R
f
value
b) Separation of amino acids

Atomic Structure

I. Atomic structure
A. Different model of atomic structure
B. Isotopic mass and relative atomic mass
1. Mass spectrometer
a) Determination of atomic mass
b) Determination of molecular mass
C. Radioactivity of nuclide
1. Nature of radioactivity
a) Penetrating power of radiation
2. Radioactive decay
a) Half life
b) Use of radioactive isotope
II. Electronic structure of atoms
A. Emission spectrum of hydrogen
1. Origin of emission and absorption spectrum
2. Pattern of energy levels of hydrogen
3. Determination of the ionization energy
a) Through the convergence limit of Lyman series
b) Through Rydberg constant
B. Detail electronic configuration
1. Definition of ionization energy
2. Successive ionization energy
3. Periodicity of First ionization energy
a) First I.E. across periods
b) First I.E. down a group
4. Quantum numbers
a) Energy of electrons in different orbitals
5. Building up of electrons in an atom
a) Aufbau principle
b) Pauli exclusion principle
c) Hund's rule
d) Building up of electrons
e) Detail electronic configuration of some atoms
6. Electronic configuration of first 36 elements
a) Extra stability of half-filled and full-filled subshell
7. Position of s-, p-, d- and f-block elements
III. Atomic orbitals
A. Shape of s, p and d orbitals
IV. Periodic Table
A. Variation in atomic radius
B. Variation in electronegativity


I. Atomic structure Unit 1 Page 1
Topic I. Atomic Structure Unit 1

Reference
Reading
1.1, 1.3
Chemistry in Context, 3rd Edition, ELBS pg. 2–4, 57–58
Physical Chemistry, 4th Edition, Fillans pg. 3–5, 10–17
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 6–12
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 1, 2,–4, 54–62

Syllabus
Different model of atomic structure
Mass spectrometer

Notes
I. Atomic Structure

A. Different model of atomic structure

Dalton’s model Thomson’s model Rutherford’s model

Bohr’s model Wave model Orbital model


Dalton’s model (1808)
Atom is a solid, indivisible sphere.
Thomson’s model (1899)
Atom is made of electrons evenly spread throughout positive mass.
Rutherford’s model (1911)
Atom is made of electrons and nucleus where most of the space is empty.
Bohr’s model (1913)
The electron is moving around the nucleus in certain circular orbits.
Wave model (1924)
The electron is moving around the nucleus in a wave like motion.
Orbital model (1927)
The exact position of the electron cannot be predicted or measured, an electron density cloud is used to describe the
probability of finding an electron in certain region.

N.B. Model is just as good as what you want it to explain.


B. Isotopic mass and relative atomic mass

Isotopic mass – The relative isotopic mass of a particular isotope of an element is the mass of one atom of that
isotope on the Carbon-12 scale. (a mass has no unit).
Relative atomic mass – The relative atomic mass of an element is the weighted average of the isotopic masses of
its natural isotopes on the Carbon-12 scale.
Carbon-12 scale – A scale in which Carbon-12 isotope is chosen as the standard and 12 units is assigned to it
by definition. The masses of other atoms are determined by comparing with this standard.


I. Atomic structure Unit 1 Page 2


1. Mass Spectrometer

A device in which particles are ionized and the accelerated ions are separated according to their mass to charge
(m/e) ratio.

Construction of Mass Spectrometer

Heater – to vaporize the sample, either element or molecule.

Ionization chamber – gas molecules are bombarded with fast speed electrons to form positive ions.
M
(g)
+ e
-
(fast) → M
+
(g)
+ 2e
-


Accelerating plate / Negatively charged plate – to accelerate the beam of positive ions across the electric field.

Magnet / Magnetic field – to deflect the ion beam, the magnetic field is adjusted so that ions of a particular
mass are focused onto the ion-detector

Detector – detect the signal and pass it on to a recorder.

Vacuum pump – to evacuate the apparatus. This allow the positive ions to travel in straight lines without collision
and prevents presence of other substances in the spectrometer that will ionize and affect the result

Knowing the magnetic field strength(B), Accelerating voltage(V) and the radius of the path(r), the mass of the ion
can be calculated. (Calculation not required.)


Important uses of Mass Spectrometer
1. Measurement of isotopic masses of an element.
2. Measurement of molecular mass.
3. Identification of compounds - the various m/e signals and peak heights are processed by computer.
4. Determination of ionization energies.


Mass Spectrum
A spectrum is obtained with a mass spectrometer, in which a beam of ion is arranged in order of increasing mass to
charge (m/e) ratio.

The detector current is directly proportional to the relative abundance of the ions reaching the detector. So by
using a mass spectrum of a sample of an element, the relative atomic mass of the element can be determined.

I. Atomic structure Unit 1 Page 3


a) Determination of relative atomic mass from mass spectrum

(Not to scale)

The four isotopes of lead are lead-204, lead-206, lead-207 and lead-208.
The height of the peak at 204 = 0.07"
The height of the peak at 206 = 1.81"
The height of the peak at 207 = 1.66"
The height of the peak at 208 = 2.81"
Total height of the four peaks = 0.07" +1.81" + 1.66" + 2.81" = 6.35"

Since, the height of the peak ∝ the relative abundance

The relative atomic mass of lead

= 204 ×
0.07"
6.35"
+ 206 ×
1.81"
6.35"
+ 207 ×
1.66"
6.35"
+ 208 ×
2.81"
6.35"
= 207(207.19)


b) Determination of molecular mass

Another important use of mass spectrometer is to determine the mass of a molecule. Similar to an atom, a molecule
will be ionized upon bombardment with fast moving electrons.
Once a molecule is ionized, it becomes energetic and unstable. It tends to break up into several fragments. Since
the fragment always has a smaller mass than the original molecule, the peak on the mass spectrum with the highest
(m/e) ratio corresponds to the original molecule.

For example, the following is the spectrum of a sample of methane CH
4
.


Ionization CH
4
+ e
-
→ CH
4
+
+ 2e
-

Fragmentation CH
4
+
→ CH
3
+
+ H and CH
3
+
→ CH
2
+
+ H etc.

Fragment
12
CH
4
+

12
CH
3
+

12
CH
2
+

12
CH
+

12
C
+

m/e 16 15 14 13 12

Besides the peak with m/e ratio 16, a very small peak (about 1% of that of 16) with m/e ratio 17 is found. It is
caused by the existence of trace amount of C-13 isotope in the nature.
I. Atomic structure Unit 1 Page 4


Carbon-12 scale

After the invention of mass spectrometer, structure of numerous number of organic molecules have been studied.
Because all organic compound contains carbon, it would be more convenient if carbon is used as the standard of
reference in mass spectrum. As a result, in 1961, C-12 was chosen as the standard for atomic mass and carbon-12
scale is established.
In carbon-12 scale, by definition, 12 g of C-12 contains 1 mole of C-12 atoms. Since the definition is solely
arbitrary, there is no wonder why Avogadro number is not a whole number. Indeed the experimental determination
of the more precise value of Avogadro number is still the interest of many scientists.

Glossary
orbital – Loosely speaking, it is used to describe the geometrical figure which describes the most probable
location of an electron. More accurately, it is used to denote the allowed energy level for electrons.

(relative) isotopic mass (relative) atomic mass Carbon–12 scale


Past Paper
Question
90 2A 3 a
96 1A 1 a i ii iii
98 2A 4 c
99 2A 1 a i

90 2A 3 a
3a Give an account of the use of a mass spectrometer for determining the relative masses of particles. 6
The modern method of determining atomic masses uses the mass spectrometer.
2 marks
- the sample (an element) is bombarded by electrons to form positively charged ions.
- the ions are accelerated by the electric field between plates A and B.
- the ions travel along until deflected by the magnetic field
- the magnetic field is adjusted so that ions of a particular mass are focused into the ion-detector
- knowing the magnetic field strength, accelerating voltage and the radius of the path, the atomic mass can be
calculated.
- the mass spectrometer responds to the mass-to-charge (m/e) of the ionized species 4 marks

C Many candidates did not point out that the mass spectrometer responds to the mass to charge ratio.
Some candidates did not know the positively charged ions are accelerated by the electric field.


I. Atomic structure Unit 1 Page 5
96 1A 1 a i ii iii
1a i Write down the number of neutrons, protons and electrons in one atom of carbon-12,
12
C, and in one atom of
carbon-13,
13
C .
1

12
C 6n, 6p, 6e ½ mark
13
C 7n, 6p, 6e ½ mark

ii The isotopic mass of
12
C is 12.000 atomic mass unit (a.m.u.). Calculate the mass, in kg, of 1 mole of
12
C atoms.
(1 a.m.u. = 1.6605 × 10
-27
kg; Avogadro constant, L = 6.0221 × 10
23
mol
-1
)
2
Mass of 1 mole of
12
C = 12.000 × 1.6605 × 10
-27
× 6.0221 × 10
23
1 mark
= (0.0119996) = 0.0120 kg 1 mark
(Accept answers which could round off to 0.012)

iii The following data were obtained from the mass spectrum of a carbon-containing compound :
Ion Mass / a.m.u. Relative intensity
12
C
+
12.000 100.00
13
C
+
13.003 1.12
Using the above data, calculate the relative atomic mass of carbon.
2

relative atomic mass =
12.000 × 100.00 + 13.003 × 1.12
(100.00 + 1.12)
1 mark
=
1214.57
101.12
= 12.011 1 mark
(Accept answers which could round off to 12.01)
(Deduct ½ mark if unit is given)

C Well answered in general, though some candidates did not give the unit, kg, as required.
Many candidates wrongly assigned the unit a.m.u. to the relative atomic mass of carbon.


98 2A 4 c
4c Sketch the expected mass spectrum for a gas sample having the composition : N
2
78%, O
2
21% and CO
2
1%.
(You only need to consider the major isotope of each element.)
3

99 2A 1 a i
1a i Rubidium occurs naturally in two isotopic forms. The table below lists the mass and relative abundance of each
isotope.

Isotope Mass / a.m.u. Relative abundance

85
Rb 84.939 72.15%

87
Rb 86.937 27.85%
(I) Suggest an experimental method to detect the isotopes of rubidium and state how the relative abundance of
each isotope can be obtained.
(II) Calculate the relative atomic mass of rubidium.


I. Atomic structure Unit 2 Page 1
Topic I. Atomic Structure Unit 2

Reference
Reading
1.2
Chemistry in Context, 3rd Edition ELBS pg. 83–89, 93–95
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 13–20
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 76–81

Syllabus
Nature of radioactivity
Radioactive decay

Notes
C. Radioactivity of nuclide

1. Nature of radioactivity
There are totally 109 elements, but owing to the presence of the isotope, there are over 1600 different nuclei. Only
238 nuclei are stable, all others exhibit some kind of radioactivity. They eject proton, neutron and electron or emit
strong electromagnetic radiation. The process is called radioactive decay and the elements are said to be
radioactive.


a) Penetrating power of radiation

There are 3 types of radioactivity.

Emission Nature Relative velocity Range in air Relative penetrating
power
α particle He nuclei (2p + 2n) 1/20 velocity of light a few cm 1
β particle fast moving electrons 3 – 99% velocity of
light
a few m 100
γ radiation electromagnetic wave 100% velocity of light a few km 10000


Penetrating power is ∝
1
mass
; ∝
1
charge
; ∝ velocity

Emission Relative mass Relative charge Relative effect of electric and magnetic field
α particle 4 units + 2 small deflection
β particle 1 / 1840 unit - 1 large deflection
γ radiation – 0 no deflection

Effect of electric field

Effect of magnetic field

(The magnetic field is going into the paper.)

The deflection is ∝ charge and ∝
1
mass


All of the three kinds of radioactivity have the ability to ionize the air, so a Geiger-counter can be used to measure
the activity of the radioactive material.
I. Atomic structure Unit 2 Page 2

2. Radioactive decay

In a nuclear reaction, unlike ordinary chemical reaction, nuclei are involved instead of electrons.

In the reaction,
1. one element can be changed to another element by radioactive decay, atomic fission or atomic fusion.
2. a large amount of energy is released in the process, the energy is from the binding energy in the nucleus.
The process in which an element changes to another element in nuclear reaction is known as transmutation.


Alpha Decay

This is a decay common to most of the radioactive
isotopes of elements with Z > 82 (Pb). (high p: n ratio)

e.g. a)
92
238
U →
2
4
He +
90
234
Th
b)
88
226
Ra →
2
4
He +
86
222
Rn
c)
88
224
Ra →
2
4
He +
86
220
Rn

When an element undergoes alpha decay, its mass no.
will be reduced by 4 and the atomic no. will be reduced
by 2.

Note: i) the charge of the particle, e.g. the charge on He
nucleus, is usually omitted for simplification. ii) the
mass number and the atomic number in all nuclear
reaction must be conserved.





Beta Decay

This is a decay common to most radioactive isotopes of elements with Z < 82. (low p: n ratio)


e.g. a)
6
14
C→
−1
0
e +
7
14
N
b)
47
108
Ag →
−1
0
e +
48
108
Cd
c)
0
1
n →
−1
0
e +
1
1
H


When an element undergoes beta decay, its mass no.
will remain unchanged and the atomic no. will increase
by 1.


Gamma Radiation

Unlike alpha and beta decay, an element emitting
gamma radiation will not change to another element. It
will only change from a high energy(excited) state to an
low(stable) energy state.

e.g. a)
90
234
Th
*
→ γ–ray +
90
234
Th


Most of the heavy isotope will undergo multiple decays
to form a series. The U-238 isotope can decay through
multiple stages to a stable Pb-206 isotope



I. Atomic structure Unit 2 Page 3
a) Half life of radioactive decay

Half life - the time taken by a given amount of radioactive isotope to decay to half of the original amount.

e.g. Radioactive Isotopes Half-life
Uranium-238 4.5 × 10
9
years
Carbon-14 5.7 × 10
3
years
Polonium-214 1.5 × 10
-4
seconds

The stability of an isotope is directly proportional to its half life.

For example, if there are 100 Uranium-238 isotopes, it will take 4.5 x 10
9
years to decay to half of the original
amount (50 Uranium-238 isotopes).

The rate of radioactive decay, unlike rate of chemical reaction, only depends on the amount of isotopes present.
The changes in external factors such as temperature and pressure have no effect on it.

Rate of radioactive decay

The rate of the decay decreases as the decay proceeds because the rate of decay is directly proportional to the
amount of isotope remains. This forms an exponential decay curve.















After 5 half-lives, the fraction remaining will be
= ½ × ½ × ½ × ½ × ½
= 0.03125
= 3.125%
I. Atomic structure Unit 2 Page 4



Artificial Transmutation of elements

Artificial transmutation reactions are usually achieved by bombarding an element with a stream of particles,
especially neutrons, protons, alpha particles and other small nuclei.

e.g.
Uranium-238 can be transmutated to Uranium-239 by bombarded with an neutron.
i.e.
92
238
U +
0
1
n →
92
239
U

The unstable Uranium-239 then decays in two stages by emitting β-particles.
i.e. a)
92
239
U →
93
239
Np +
−1
0
e
b)
93
239
Np →
94
239
Pu +
−1
0
e

In nature the,
7
14
N in air, is transmutated to
6
14
C by the neutron from the cosmic ray (fast moving neutron).
i.e.
7
14
N +
0
1
n →
6
14
C+
1
1
H

In some cases, if the speeds of intruding neutrons are different, it will cause different modes of nuclear reaction.
e.g. a)
13
27
Al +
0
1
n →
11
24
Na +
2
4
He
b)
13
27
Al +
0
1
n →
12
27
Mg +
1
1
p
c)
13
27
Al +
0
1
n →
13
28
Al + γ-ray


b) Use of radioactive isotope
1. Treatment of cancer
2. Study of metabolic pathways.
3. Thickness gauges and empty packet detection.
4. Archaeological and geological dating.
5. Sterilizing surgical instruments.
6. Detection of leakage. (e.g. water pipes)

Glossary
nuclide - A type of atom specified by its atomic number, atomic mass, and energy state, such as carbon 14.
penetrating power radioactive decay half-life

I. Atomic structure Unit 2 Page 5

Past Paper
Question
91 2A 1 a i ii
93 1A 1 a i ii
95 2A 2 a i
99 1A 2 b i ii

91 2A 1 a i ii
1a
The radioactive decay of
92
238
U may be represented by
92
238
U →
82
206
Pb + α + β.

i State the nature of α and β particles and compare their penetrating power. 3
α particles are bare helium nucleus with two positive charge and four units of mass. 1 mark
β particles are fast electrons, which is negatively charged. 1 mark
The penetrating power of β particles is 100 times stronger than α particles. 1 mark

ii Balance the above equation. 2

92
238
U →
82
206
Pb + 8
2
4
He + 6
−1
0
e 2 marks

C Many candidates incorrectly stated that α particles are helium atoms.
Some candidates did not emphasize that the electrons in β particles are moving very fast.


93 1A 1 a i ii
1a Name the particles X and Y in the following nuclear reactions, and gives their charge and mass.
Compare the action of a magnetic field upon the paths of X and Y
4
i
90
229
88
225
Th X Ra → + X is _______________

X is / helium nucleus / α particle 1 mark
ii
88
225
89
225
Ra Y Ac → + Y is _______________

Y is / fast moving electron / β particle. 1 mark

The path of α and β particles are deflected/bent by a magnetic field 1 mark
but they are deflected in opposite direction. 1 mark
OR by a diagram
The magnetic field is going into the paper.
Bent motion 1 mark
Correct direction 1 mark


95 2A 2 a i
2a
88
228
Ra decays by the emission of β particles. The half-life for the decay is 6.67 years.

i
Write a balanced equation to represent the decay of
88
228
Ra .
1

88
228
Ra →
89
228
Ac +
−1
0
e 1 mark

C Many candidates did not make use of the Periodic Table given in the question paper to find the symbol (Ac) for
the product of the decay, and hence they arrived at incorrect answers.


99 1A 2 b i ii
2b Radioactive decay of radium (Ra) in rocks and soil produces radioisotopes of radon (Rn). One of the isotopes
86
222
Rn decays to give
84
218
Po with a half-life of 3.82 days.

i
Write the nuclear equation for the decay of
86
222
Rn .

ii
Explain why
86
222
Rn is considered hazardous to health.


II. Electronic Structure of atoms Unit 1 Page 1
Topic II. Electronic Structure of atoms Unit 1

Reference
Reading
2.1
Chemistry in Context, 3rd Edition ELBS pg. 69–71
Physical Chemistry, 4th Edition, Fillans pg. 63–74
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 31–36
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 64–68

Syllabus
Emission spectrum of hydrogen
Determination of ionization energy

Notes
II. Electronic Structure of atoms

A. Emission spectrum of hydrogen

Emission Spectroscopy
White light from tungsten lamp consists of a continuous range of wavelengths of visible light. The white light can
be separated into different colour light by a prism and forms a continuous spectrum of visible light, like a rainbow.

But some lights, for example, the light from the sodium lamp or green light from the flame test of copper, are not
composed of a continuous range of wavelengths, instead they are only mixtures of a limited number of
wavelengths. In this case, the spectrum is known as a line spectrum.

1. Origin of emission

Emission spectrum

i. At room temperature, nearly all the atoms in a given sample of substance are in the ground state, the electrons
occupy the orbital of lowest energy. The atom is in the ground state because all electrons in the atoms are
having the lowest possible energy.

ii. Energy is given to the atoms by heating the element with Bunsen flame or hitting with electrons in discharge
tube. The electrons takes up the energy and are promoted to a higher energy state, excited state.
iii. Since the electrons in excited state are not stable, they tends to fall back to a lower energy state to dissipate
their extra energy in form of radiation. Each transition involves a definite amount of energy, called a quantum.
iv. Different transition has different energy and each transition corresponds to a single line in the emission
spectrum. The greater the number of electrons making a particular transition, the more intense the spectral line
is. This gives coloured emission lines on dark background.
v. The relationship between the wavelength(λ) and frequency(υ) of any electromagnetic radiation is given by
λ =
c
υ
where c is the velocity of light
vi. And, the relationship between energy of radiation is given by the equation

∆E = hυ where h is Planck’s constant and υ is frequency
II. Electronic Structure of atoms Unit 1 Page 2


2. Pattern of energy levels of hydrogen

Balmer series

i. The emission line spectrum of hydrogen atom consists of many lines, some of them fall in the visible region
and some of them fall in the invisible region.
ii. The visible part of the spectrum was first studied by the scientist Balmer. This series of spectrum lines was
named after him as Balmer series.

iii. The red line, the line with longest wavelength in the visible region, corresponds to the transition of an electron
from the third energy level (n=3) to the second energy level (n=2). It gives out a quantum of light, called
photon. With increasing frequencies, the lines get closer and closer until they merge, this is because the
difference between energy levels gets smaller as the frequency increases.


Relationship between emission spectrum and energy levels


iv. The point, where the spectral lines merge, corresponds to the electron transition between energy levels with n
= ∞ and n = 2.
v. At n = ∞, the electron has effectively left the atom. That means the atom has been ionized.



II. Electronic Structure of atoms Unit 1 Page 3


Complete Hydrogen Emission Spectrum



i. Besides Balmer series, the complete spectrum is composed of many series. The origin of other series is similar
to that of Balmer series, the only difference is the destination of the electrons.



ii. Bohr obtained an expression for the frequencies of the lines in the spectrum.
υ = − cR
n n
H
( )
1 1
1
2
2
2
where R
H
is Rydberg constant
c is velocity of light

n
1
and n
2
are integers, called principal quantum number, with n
2
greater than n
1
.
n
1
: the principal quantum number of the energy level to which the electron returns.
n
2
: the principal quantum number of the energy level from which the electron leaves.


II. Electronic Structure of atoms Unit 1 Page 4


3. Determination of the ionization energy

The ionization energy of hydrogen can be determined by measuring the frequency the convergence limit (υ
∞→1
) of
Lyman series or by determining the Rydberg constant through the frequency of a specific line.

a) Through the convergence limit of Lyman series

Ionization of hydrogen = ∆E = h υ
∞→1


However, it is quite difficult to determine the convergence limit accurately as the lines are getting close
together when approaching the convergence limit and the spectrum becomes a bright continum beyond the
limit. Therefore, the limit is usually determined graphically.


i. In Lyman series, there is a convergence limit in the line spectrum. It
represents the point where the difference in energy levels diminished.
ii. The frequencies of the first lines in Lyman series are measured. The
differences in frequencies between two adjacent lines are calculated.
e.g. ∆υ
1
= (υ
2
- υ
1
), ∆υ
2
= (υ
3
- υ
2
) ...iii. A graph of υ against ∆υ is
plotted.
iv. The curve is extrapolated, and the υ at y-intercept, where ∆υ = 0, will
correspond to the transition of electron from n = ∞ to n = 1.
v. The Ionization energy can be calculated by I.E. = hυ







b) Through Rydberg constant

For example, the Rydberg constant can be determined by measuring the frequency of the first line of Lyman
series (υ
2→1
). Thereafter, by applying the Ryberg equation, the ionization energy of hydrogen can be
calculated.

i. The Rydberg constant is calculated from the first line in the Lyman series.
υ
2 1 2 2
1
1
1
2

= − cR
H
( )
ii. The frequency corresponding to the ionization process is calculated by

υ
∞→
= −

1 2 2
1
1
1
cR
H
( )
iii. The ionization energy(I.E.), the energy transition from the ground state and the continuum for one
electron is
Ionization energy(I.E.) = h υ
∞→1

= hcR
H

The ionization energy per mole = LhcR
H
where L is the Avogadro's constant


Glossary
emission spectrum absorption spectrum Planck’s constant Balmer series Lyman series
Paschen series Rydberg equation


II. Electronic Structure of atoms Unit 1 Page 5

Past Paper
Question
90 2A 2 c
95 1A 1 b i ii
97 2A 2 a
99 1A 2 a i ii

90 2A 2 c
2c Give a brief account for the Balmer series in the spectrum of the hydrogen atom. 4
It is a series of lines resulting from photons emitted or absorbed by the hydrogen atom with wavelength in the
visible region. These spectral lines are the result of transitions of the electron from one energy level to another
with the lower energy level with quantum number n
1
= 2. 2 marks
The wavelengths of this series satisfies the formula,
1
λ
= R
H
(
1
2
2 -
1
n
2
2) 1 mark
where R
H
is the Rydberg constant
n
2
= 3,4,5 ...
λ = wavelength 1 mark

C Many candidates gave the correct formula for the relationship between wavelength and quantum numbers, but
only a few defined their symbols.


95 1A 1 b i ii
1b i What can you deduce from the fact that the spectral lines in the atomic emission spectrum of hydrogen are not
equally spaced ?
1
The energy differences between electron shells in a hydrogen atom are not the same (converge). 1 mark
ii In the atomic emission spectrum of hydrogen, the convergence limit for the Lyman series occurs at 3.275 x 10
15

Hz. Calculate the ionization energy of hydrogen, in kJ mol
-1

(Planck constant, h = 6.626 x 10
-34
J s; Avogadro constant, L = 6.023 x 10
23
mol
-1
)
2
I.E. = hυ
= (6.26 × 10
-34
) × (3.275 × 10
15
× 6.023 x 10
23
) 1 mark
= 1.307 × 10
6
Jmol
-1
/ 1307 kJmol
-1
1 mark

C Many candidates were unable to point out that the energy differences between two energy levels are not the same
and hence the spectral lines in the emission spectrum are not equally spaced. Many candidates neglected to give
the answer to (ii) in kJmol
-1
.


97 2A 2 a
2a Describe and account for the characteristics of the emission spectrum of atomic hydrogen. 7

99 1A 2 a i ii
2a i Outline the origin of atomic emission.
ii Briefly explain why each series of atomic emission lines of hydrogen converges at the lower wavelength end.
(3 marks)


II. Electronic Structure of atoms Unit 2 Page 1
Topic II. Electronic Structure of atoms Unit 2

Reference
Reading
2.2–2.3
Modern Physical Chemistry ELBS pg. 26–33, 39–41
Chemistry in Context, 3rd Edition ELBS pg. 71–78
Physical Chemistry, 4th Edition, Fillans pg. 74–77, 80–84, 88–95
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 37–42, 49–53
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 38–42, 64, 68–71, 73–74, 170, 173–175

Syllabus
Detail electronic configuration

Notes
B. Detail electronic configuration

1. Definition of first ionization energy

X
(g)
→ X
+
(g)
+ e
-


First ionization energy – Energy required to remove an electron from a free atom in gaseous state.
Normally measured in electron volts (eV) or kJmol
-1
.
(1eV = charge of electron × 1V = 1.60 × 10
-19
C × 1V = 1.60 × 10
-19
J)

2. Successive ionization energy (presence of electron shells)

The information from successive ionization energy can be used to deduce the electronic configuration of an atom.

The ionization of Potassium (K) can take place in steps

1st ionization
K
(g)
→ K
+
(g)
+ e
-
∆H
I1
= 419 kJmol
-1

2nd ionization
K
+
(g)
→ K
2+
(g)
+ e
-
∆H
I2
= 3051 kJmol
-1

3rd ionization
K
2+
(g)
→ K
3+
(g)
+ e
-
∆H
I3
= 4412 kJmol
-1


i. The value of successive ionization energy increases as more electrons are removed from the atom. This is
because extra energy is needed to removed an electron from an ion of increasing positive charge.


ii. The 2nd I.E. is much higher than 1st I.E. It can be observed from the graph that the I.E.s of K atom can be
divided into 4 groups. 1 in the first group, 8 in the second group, 8 in the third group and remaining 2 in the
fourth.
iii. This indicates that a K atom has four electron shells and electronic configuration of 2,8,8,1.
II. Electronic Structure of atoms Unit 2 Page 2

3. Periodicity of First ionization energy (presence of electron sub-shell)

a) First I.E. across periods


First ionisation Energy of the first 38 elements

i. The 1st I.E. increases roughly across a period due to the increase in nuclear charge.
ii. Besides the main trends, some irregularities are found within a period. This suggests the presence of sub-
shells (s, p, d and f sub-shells) within an electron shell (n = 1, 2, 3 ...)
iii. In period 2 and 3, the increasing trends can further be broken up into 3 parts, in a 2-3-3 manner. This suggest
the presence of subshells.
iv. In period 4, from K to Kr, the trend can be broken into 4 parts, in a 2-10-3-3 manner. This suggest the
presence of another set of subshells.


b) First I.E. down a group

Li
Na
K
Rb
Cs
350
370
390
410
430
450
470
490
510
530
F
i
r
s
t

I
.
E
.

/

k
J
m
o
l
-
1

F
Cl
Br
I
900
1000
1100
1200
1300
1400
1500
1600
1700
F
i
r
s
t

I
.
E
.

/

k
J
m
o
l
-
1

He
Ne
Ar
Kr
Xe
1000
1200
1400
1600
1800
2000
2200
2400
F
i
r
s
t

I
.
E
.

/

k
J
m
o
l
-
1


1st I.E. of group I 1st I.E. of group VI 1st I.E. of group 0

i. On down a group, the 1st I.E. decreases as the number of electron shells or the size of the atom increases. The
attraction between the outermost electron and the nucleus decreases with increasing atomic size.


II. Electronic Structure of atoms Unit 2 Page 3

A prevailing explanation for these variation in ionization energy is that different electrons occupy different orbitals
in an atom. Since different orbitals have different energies, the electron in different orbital shows difference in
energy. A more energetic electron would be removed more readily and has a lower ionization energy.


4. Quantum numbers

To facilitate the discussion of the detail electronic configuration of an atom, a set of four quantum numbers is
assigned to each electron in an atom.
Quantum numbers is the I.D. no of the electron in an atom.

The four quantum numbers are

Allowed value
Principal quantum number (n) specify the principal energy level. Any natural number

Subsidiary quantum number (l)
specify the shape of the orbital. Depends on n, in the range of 0, 1,
2 .. (n-1)
Magnetic quantum number (m) specify the direction of the orbital.
Depends on l, in the range of -l to
+l
Spin quantum number (s) specify the spin of the electron. Either +½ or -½


Electrons with different subsidiary quantum numbers can be denoted by the letters s, p, d and f, or s orbital, p
orbital, d orbital and f orbital.

l = 0, 1, 2, 3
s p d f

a) Energy of electrons in different orbitals



i. The principal quantum no. (n) determines the principal energy level of the orbital.
ii. With the same principle quantum no. (n), the energy of orbitals increases in following order, s < p < d < f.
iii. The energy of orbitals is independent of magnetic quantum number (m) and spin quantum number (s).
iv. The orbitals are labelled according to the values of n, l and m.
e.g. The orbitals with n = 2, l = 1 and m = 1, 0 and -1 are called 2p
x
, 2p
y
and 2p
z
orbitals.
II. Electronic Structure of atoms Unit 2 Page 4


5. Building up of electrons in an atom

a) Aufbau principle
In building up the electronic configuration of an atom in its ground state, the electrons are placed in the
orbitals in order of increasing energy

b) Pauli exclusion principle – In any atom, no two electrons can have all four quantum numbers the same.

c) Hund’s rule (Rule of maximum multiplicity)
Electrons in degenerate orbitals will occupy each orbital singly before electron pairing takes place.

To generalize the three rules, the following procedure of filling the orbitals shown be observed

i. Of the available orbitals, the added electron will always occupy the one with the lowest energy. (Aufbau
principle)
ii. Each orbital may hold only two electrons, and they must have opposite spin. (Pauli exclusion principle)
iii. Where a number of orbitals of equal energy are available, the added electron will go into empty orbital,
keeping electron spins the same, before spin-pairing occurs. (Hund's rule)

According to the Aufbau principle, the electrons will fill the available orbitals with lowest energy first. The order
of energy levels need not to be exactly parallel to the principal quantum. When the atom becomes heavy, the
high energy levels tend to overlap each other. For example, the energy of 4s orbital is lower than that of 3d orbital.



II. Electronic Structure of atoms Unit 2 Page 5




The order of energy of the orbitals can be predicted by
the pattern shown on the left.

The order of the energy levels mainly depends on the
attraction between the orbital and the nucleus. The
stronger the attraction, the lower will be the energy of
the orbital. (because of lower potential energy)

This once again depends on the spatial distribution of
the orbital.





Spatial distribution of 3s and 3p orbitals

Moreover, from the fact that 4s orbital is less energetic than 3p
orbital. The effect of penetration of penetration must be more
significant than the effect of distance and shielding effect.
For example, 3s orbital has lower energy
than 3p orbital because

i. Distance from the nucleus
3s orbital is closer to the nucleus than 3p
orbital, thus the 3s orbital will experience
more attraction.

ii. Penetration of 3s orbital
Spatial distribution of 3s orbital has 2 small
peaks close to the nucleus and make it
experience more attraction.

iii. Shielding / Screening effect
Besides attraction with the nucleus, 3p
electrons also experience repulsion will K-
shell, L-shell and 3s electrons. This is
known as shielding / screening effect of
inner electrons.


Note : The completely filled shell can be denoted by K, L, M, N according to the principal quantum no





Shielding effect and effective nuclear charge

Owing to shielding effect, the electrons in an atom experience attraction from the nucleus less than the actual
nuclear charge. The effective nuclear charge is always less than actual nuclear charge.

There is two kinds of shielding effect

Primary shielding effect
This is stronger than the secondary shielding effect. This is the shielding effect of the inner electrons on the outer
electrons from the nucleus. i.e. electrons in shells of lower principal quantum number are more effective shields
than electrons in shells of higher quantum number and s-orbital electrons is more effective in shielding than p
orbital electrons.

Secondary shielding effect
The shielding effect of the electrons/repulsion between electrons in the same orbital. This is much weaker than
primary shielding effect.

II. Electronic Structure of atoms Unit 2 Page 6


d) Building up of electrons

i. The quantum no. of the electron in hydrogen atom in ground state

n = 1, l = 0, m = 0, s = +½

1s
1 electron in box 1s
1


Electron with spin quantum no. +½ is represented by an upward arrow.


ii. The quantum no. of the two electrons in helium atom in ground state

n = 1, l = 0, m = 0, s = +½
n = 1, l = 0, m = 0, s = -½

1s
2 electron in box 1s
2



iii. The quantum no. of the three electrons in lithium atom in ground state

n = 1, l = 0, m = 0, s = +½
n = 1, l = 0, m = 0, s = -½
n = 2, l = 0, m = 0, s = +½

1s 2s
0 0 1s
2
2s
1



iv. The quantum no. of the six electrons in carbon atom in ground state


n = 1, l = 0, m = 0, s = +½
n = 1, l = 0, m = 0, s = -½
n = 2, l = 0, m = 0, s = +½
n = 2, l = 0, m = 0, s = -½
n = 2, l = 1, m = 1, s = +½
n = 2, l = 1, m = 0, s = +½

1s 2s 2p
0 0 000 1s
2
2s
2
2p
2




e) Detail electronic configuration of some atoms

i. The electronic configuration of argon atom in ground state

1s 2s 2p 3s 3p
0 0 000 0 000 1s
2
2s
2
2p
6
3s
2
3p
6


II. Electronic Structure of atoms Unit 2 Page 7


ii. The electronic configuration of potassium atom in ground state

1s 2s 2p 3s 3p 4s
0 0 000 0 000 0 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1



iii. The electronic configuration of scandium atom (Z=21) in ground state

1s 2s 2p 3s 3p 3d 4s
0 0 000 0 000 00000 0

1s
2
2s
2
2p
6
3s
2
3p
6
3d
1
4s
2
or [Ar]3d
1
4s
2
or K L 3s
2
3p
6
3d
1
4s
2


Note : Writing of electronic configuration follows the principal quantum no., not the order of placing electrons


iv. The electronic configuration of germanium atom (Z=32) in ground state

1s 2s 2p 3s 3p 3d 4s 4p
0 0 000 0 000 00000 0 000

1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
2
or [Ar]3d
10
4s
2
4p
2
or K L M 4s
2
4p
2



6. Electronic configuration of first 36 elements


1 H 1s
1

2 He 1s
2

3 Li 1s
2
2s
1

4 Be 1s
2
2s
2

5 B 1s
2
2s
2
2p
1

6 C 1s
2
2s
2
2p
2

7 N 1s
2
2s
2
2p
3

8 O 1s
2
2s
2
2p
4

9 F 1s
2
2s
2
2p
5

10 Ne 1s
2
2s
2
2p
6

11 Na 1s
2
2s
2
2p
6
3s
1

12 Mg 1s
2
2s
2
2p
6
3s
2

13 Al 1s
2
2s
2
2p
6
3s
2
3p
1

14 Si 1s
2
2s
2
2p
6
3s
2
3p
2

15 P 1s
2
2s
2
2p
6
3s
2
3p
3

16 S 1s
2
2s
2
2p
6
3s
2
3p
4

17 Cl 1s
2
2s
2
2p
6
3s
2
3p
5

18 Ar 1s
2
2s
2
2p
6
3s
2
3p
6

19 K 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1

20 Ca 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2

21 Sc 1s
2
2s
2
2p
6
3s
2
3p
6
3d
1
4s
2

22 Ti 1s
2
2s
2
2p
6
3s
2
3p
6
3d
2
4s
2

23 V 1s
2
2s
2
2p
6
3s
2
3p
6
3d
3
4s
2

24 Cr 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
1

25 Mn 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
2

26 Fe 1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2

27 Co 1s
2
2s
2
2p
6
3s
2
3p
6
3d
7
4s
2

28 Ni 1s
2
2s
2
2p
6
3s
2
3p
6
3d
8
4s
2

29 Cu 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
1

30 Zn 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2

31 Ga 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
1

32 Ge 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
2

33 As 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
3

34 Se 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
4

35 Br 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
5

36 Kr 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6



a) Extra stability of half-filled and full-filled subshell

It can be observed that Cr (Z=24) and Cu (Z=29) do not follow the general trend.
Instead of [Ar]3d
4
4s
2
, Cr has the electronic configuration [Ar]3d
5
4s
1

Instead of [Ar]3d
9
4s
2
, Cu has the electronic configuration [Ar]3d
10
4s
1


Extra stability is associated with i. half-filled orbital and ii. completely/full-filled orbital.
This is because i. a half-filled or full-filled d orbitals mean an even distributed electrons in an atom which make
the electron repulsions weaker.
ii.4s
2
is less favorable than 4s
1
as pairing up of the 4s electrons creates greater repulsion between
the 2 electrons.

This also accounts for the anomaly of first I.E. of Be and N in period 2. Be has a full-filled 2s orbital and N has a
half-filled 2p orbital.


II. Electronic Structure of atoms Unit 2 Page 8


7. Position of s-, p-, d- and f- block elements
According to the electronic structure of elements, the periodic table can be divided into different blocks.

s-block elements : Group IA to Group IIA e.g. Na 1s
2
2s
2
2p
6
3s
1

p-block elements : Group IIIA to Group VIIA e.g. N 1s
2
2s
2
2p
3

d-block elements : Transition metal e.g. Mn 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
2

f-block elements : Lanthanide and Actinide e.g. Pr 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
4f
3
5s
2
5p
6


Across the s-block, electron is being added into the s sub-shell. While moving across, p-, d- and f- block, the
electron is added into the p, d and f sub-shell.

Glossary
First ionization energy electron shell /orbital electron sub-shell/sub-orbital quantum number
Aufbau principle Pauli exclusion principle Hund's rule
degenerate orbitals – orbitals with the same energy penetration shielding / screening effect
effective nuclear charge electron in box half-filled orbital full-filled orbital s-block p-block d-block
f-block transition metal

Past Paper
Question
90 2B 4 a
92 2A 1 a ii iii
93 1A 2 a v
95 1A 1 a i 95 2B 5 a iv 95 2B 6 a
96 1A 1 c i ii
97 2A 2 b i ii iii
98 1A 1 a 98 2B 8 a

90 2B 4 a
4 Account for the following observations.
4a The first ionization energies of the second row elements are in the order Li < B < Be < C < O < N < F < Ne. 4
Increase in effective nuclear charge with full explanation, i.e. no. of protons increase 1 mark
From Li to Ne, electrons are added in the same principal shell, the shielding effect involved is only a secondary
one 1 mark
Extra stability, Be > B 1s
2
2s
2
filled 2s orbital; stability 1 mark
N > O 1s
2
2s
2
2p
3
half-filled electronic configurations; half-filled stability 1 mark

C Some candidates failed to mention or explain the abnormally high ionization potentials of Be and N.

II. Electronic Structure of atoms Unit 2 Page 9
92 2A 1 a ii iii
1a ii Arrange the following elements in order of increasing first ionization energy : F, Ne and Na. Explain your order. 2½
Na < F < Ne 1 mark
Na has the least I.E. because there is a single 3s-electron which is not strongly attracted towards the nucleus and
losing it would accomplish the completed K- and L- shell status. It is for this reason that an electron in Ne
requires the highest I.E. To lose an electron means that the F atom would move further away from the K- and L-
shell status and this requires a relatively high I.E. 1½ mark

iii Describe and explain the variation of the successive ionization energies of potassium. 3
There is a gradual increase in the successive ionization energies in general because the nucleus becomes
effectively more positively-charged as each electron is being lost. The increase is greatest when the 2nd electron
are being ionized, suggesting the 2nd electron is closer to the nucleus than the first. Similar greater but less abrupt
I.E.’s occur when the 10th and 18th electrons are being ionized.

3 marks


93 1A 2 a v
2a Answer the following questions by choosing in each case one of the species listed below, putting it in the box and
giving the relevant equation(s).
Al
(s)
, AlCl
3(s)
, AlO
2
-
(aq)
, Na
(s)
, CO
3
2-
(aq)
, Cu
2+
(aq)
, P
4
O
10(s)
, S
(s)
, S
2
O
3
2-
(aq)
, Zn
2+
(aq)


v Which species has the following ionization energies: 1st 500; 2nd 4600; 3rd 6900; 4th 9500 kJmol
-1
? 1
Na
(s)
1 mark

95 1A 1 a i
1a i The first four successive ionization energies of an element A are 578, 1817, 2746 and 10813 kJ mol
-1
respectively.
To which group in the Periodic Table does A belong ?
1
Group III / IIIA / 3 / 3A 1 mark

95 2B 5 a iv
5a The table below lists some properties of the alkali metals.
Element Atomic
radius / nm
Ionic radius / nm First ionization
energy / kJmol
-1

Standard electrode
potential / V
Melting point / ºC
Li 0.123 0.060 520 -3.04 180
Na 0.157 0.095 495 -2.71 98
K 0.203 0.133 418 -2.92 64
Rb 0.216 0.148 403 -2.93 39
Cs 0.235 0.169 374 -2.95 29
iv Explain the trend in the first ionization energy from Li to Cs. 2
The atomic radius increases as the group is descended hence the outer-shell electrons become less strongly held
and it is easier to remove an e
-
from the gaseous atom of the element. 2 marks

C iv the effective attractive forces on the electron is greatest in the case of the smallest first atom.

95 2B 6 a
6a Write the electronic configuration of a titanium atom in its ground state.
1s
2
2s
2
2p
6
3s
2
3p
6
3d
2
4s
2

3d 4s
[Ar]
11000 2
1 mark
(accept any correct form of electronic configuration)


II. Electronic Structure of atoms Unit 2 Page 10
96 1A 1 c i ii
1c Explain why
i the first ionization energy of oxygen is greater than that of sulphur; 1
S has 1 more e
-
shell / has a large atomic size than O, ½ mark
the attraction experienced by the outermost electron is smaller hence S has a smaller I.E. ½ mark
(DO NOT accept explanations in terms of effective nuclear charge; deduct ½ mark for any misconception)

C The question was poorly answered. Many candidates incorrectly attributed the difference in ionization energies to
effective nuclear charge and/or screening effect. In fact, the effective nuclear charge experienced by the outermost
shell electrons of sulphur was greater than that of oxygen. Such answers reflected the fact that many candidates
did not fully understand the concepts associated with screening effect and effective nuclear charge.

ii the first ionization energy of oxygen is smaller than that of fluorine. 1
F has 1 more proton in the nucleus, ½ mark
the effect of increase in nuclear charge has outweighed the screening effect of the additional electron hence F has
a greater I.E. ½ mark
Or,
Effective nuclear charge experienced by outermost e
-
of atom increases across a period. ∴ outermost e
-
of O is
more easily removed than that of F. 1 mark

C Many candidates pointed out that the outermost shell electron of fluorine experiences a greater effective nuclear
charge. But they explained their answers rather vaguely. This again showed that they did not grasp these concepts
well but just produced their answers by citing some terms learnt in their lessons. Some candidates incorrectly
explained the difference in ionization energies between O and F in terms of electronegativity.


97 2A 2 b i ii iii
2b i What is an electron shell in an atom ? 6
ii For each of the electron shells with principal quantum numbers 1, 2 and 3 list the subshells.
iii Deduce the maximum number of electrons in each of the electron shells in (ii).

98 1A 1 a
1a Arrange the following chemical species in the order of increasing ionization enthalpy. Explain your arrangement.
N
+
, N and O
3

98 2B 8 a
8a Which of the following, (I) or (II), is the ground state electronic configuration of chromium atom ? Explain your
answer.
3d 4s
(I) [Ar] 11111 1
(II) [Ar] 11110 2
2

III. Atomic orbitals Page 1
Topic III. Atomic orbitals

Reference
Reading
Modern Physical Chemistry ELBS pg. 41–42
Physical Chemistry, 4th Edition, Fillans pg. 78–80
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 39–40
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 72

Syllabus
2.4
Shape of atomic orbitals

Notes
III. Atomic orbitals

In the orbital model of atom, the electrons are moving in a wave like motion. Because of its extremely small mass,
the position of individual electron cannot be located precisely by any phyical mean, an electron density diagram is
therefore used to described the distribution of electrons. Atomic orbital is the region within which there is a high
probability, i.e 90%, of finding an electron. Different orbital have different shape, size and energy.

A. Shape of s, p and d orbitals


s orbital



s-orbital is spherical in shape.
The electron density at the nucleus is zero.
For 1s orbital of hydrogen, the electron density (probability density of finding a electron) increases as
the distance from the nucleus increases and reaches a maximum at a distance equal to Bohr’s radius.
And then, the electron density decreases as the distance from the nucleus increases.



p orbital



p-orbital is dump bell in shape.
The three p orbitals are perpendicular to each other. The three p-
orbitals have the same energy (degenerate).

d orbital

There are 5 degenerate d-orbitals.
d
xy
, d
xz
and d
yz
orbitals lie on xy, xz and yz plate respectively.
d
x
2
-
y
2
orbital lies on xy plate with the lobes are directing to the x and
y axes.
d
z
2
orbital looks like p
z
orbital but with a ring at the centre.

Glossary
probability density degenerate s orbital p orbital d orbital

III. Atomic orbitals Page 2

Past Paper
Question
91 2A 3 c
92 1A 2 c
96 1A 1d

91 2A 3 c
3c Give a brief account of the electron density of the 1s orbital of a hydrogen atom. 4
1s orbital is spherical in shape, the variation is exactly the same in any direction from the nucleus. At a certain
distance from nucleus, there is a maximium probability of electron density. (The most probable distance of the
electron from the nucleus of the hydrogen atom is equal to the Bohr’s radius.) The electron density is zero at the
nucleus and at infinite distance from the nucleus.


C Most candidates were able to give the correct shape of the 1s orbital, however, they failed to describe the variation
of electron density as a function of distance from the nucleus.


92 1A 2 c
2c Give the shape of a 1s-orbital and comment on its physical significance. 2
1s-orbital is spherical. ½ mark
Physical Significance
- The probability of finding an electron at various points in space is called an orbital. ½ mark
- For a give 1s-orbital, the region of highest probability of finding the electron, say 90% of the charge
distribution is pictorially represented by a single surface along which the probability of finding the electron is
constant. ½ mark
- They should be thought of as shapes with fuzzy and indistinct edges, like a cloud. ½ mark

C Only a handful of candidates were able to explain clearly the meaning of the spherical shape of the 1s-orbital and
its physical significance, i.e. the most simple description of the surface of the sphere represents the probability of
finding, say 90 %, of the 1s-electron. A majority of the candidates did not make the important point that orbitals
should be thought of as shapes with fuzzy and indistinct edges, like clouds in reality.


96 1A 1d
1d Sketch the pictorial representation of a p orbital and indicate the location of the nucleus in your diagram. 1

nucleus

(or along any axis) 1 mark

C Many candidates did not do what the question asked for and drew three p-orbitals instead of one.

IV. Periodic Table Page 1
Topic IV. Periodic Table

Reference
Reading
Modern Physical Chemistry ELBS pg.
Chemistry in Context, 3rd Edition ELBS pg. 37-41
Physical Chemistry, 4th Edition, Fillans pg. 85–88
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 111–112, 334–335
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 170–171, 175–176

Syllabus
2.5
Variation in atomic radii
Variation in electronegativity

Notes
IV. Periodic Table

A. Variation in atomic radius

Covalent radius – Half of the distance between two nuclei in an element where the atoms are chemically
combined together.
Van der Waals’ radius – Half of the distance between two nuclei in an element where the atoms are not
chemically combined together.

If not specified, atomic radius is normally referring to covalent radius. However, for those atoms where formation
of chemical bond is impossible, atomic radius will be referring to van der Waals’ radius.




a) Factor affect the size of atomic radius

proton to electron ratio (p/e) – An increase in this ratio causes an increase in effective nuclear charge,
resulting a contraction of the electron cloud of the ion. The ionic radius of
a cation is, of course, smaller than the atom itself.

Across a period – Atomic size decreases as atomic number increases. All electrons go into the same quantum
shell and the increase in nuclear charge is not effectively shielded. Effective nuclear charge
increases across a period and has a greater attraction on the outermost electrons drawing
them closer to the nucleus.

Down a group – Atomic size increases as no. of electron shells increases. The electron in the outermost shell
is effectively shielded from the nucleus by the inner electrons.

IV. Periodic Table Page 2



Variation of atomic radii



B. Variation in electronegativity



Electronegativity is a measure of tendency of an atom in a stable molecule to
attract electrons within a bonds.

Therefore, it is closely related to the effective nuclear charge experienced by the
bonding electrons.



The scientist Pauling computed a scale of electronegativity according to bond dissociation energies, ionization
energy and electron affinity values of an atom.

In Pauling scale, 4 is assigned to the most electronegative atom, fluorine.


Pauling electronegativity values of some elements (The shaded ones are more electronegative than C)

H
2.1

Li
1.0
Be
1.5
B
2.0
C
2.5
N
3.0
O
3.5
F
4.0
Na
0.9
Mg
1.2
Al
1.5
Si
1.8
P
2.1
S
2.5
Cl
3.0
K
0.8
Ca
1.0
_ Ge
1.8
As
2.0
Se
2.4
Br
2.8
Rb
0.8
Sr
1.0
_ Sn
1.8
Sb
1.9
Te
2.1
I
2.5
Cs
0.7
Ba
0.9


In general, electronegativity values increase from left to right across each period and decrease down each group.


Noble gases do not has any value of electronegativity because they do not form any stable molecule at all.


Glossary
atomic radius covalent radius van der Waals radius proton to electron ratio electronegativity

IV. Periodic Table Page 3

Past Paper
Question
89 2B 4 d ii
92 2A 3 b i ii
95 2B 5 a I

89 2B 4 d ii
4d Comment on the relative oxidizing properties of
ii the non-metal C, N, O and F. 3
C < N < O < F 1 mark
- increase in electron affinity / electronegativity from C to F
- decrease in atomic size
- 2p electrons are less effectively shielded
- increase in nuclear charge
- F is particularly reactive because of the weak F–F bond due to lone pair-lone pair repulsion 2 marks


92 2A 3 b i ii
3b i Define the covalent radius of an atom. 1
The covalent radius is defined as on-half the distance between two atoms of the same kind held together by
covalent bond. 1 mark

ii State and explain the trends in the covalent radius on going down any group and going across a short period of the
periodic table.
2
Going down any group of the periodic table the covalent radius increases ½ mark
because the elements become larger as the no. of electron increases. ½ mark
Going across any period the covalent radius decreases ½ mark
because the nuclear charge increases. ½ mark


95 2B 5 a i
5a The table below lists some properties of the alkali metals.
Element Atomic
radius / nm
Ionic radius / nm First ionization
energy / kJmol
-1

Standard electrode
potential / V
Melting point / ºC
Li 0.123 0.060 520 -3.04 180
Na 0.157 0.095 495 -2.71 98
K 0.203 0.133 418 -2.92 64
Rb 0.216 0.148 403 -2.93 39
Cs 0.235 0.169 374 -2.95 29
i Explain why the atomic radii increase from Li to Cs. 1
As the group is descended, the next atom has another shell of electrons around the nucleus, therefore larger the
atomic radius. 1 mark

C as the group is descended, the 'next' atom has one more shell of electrons around the nucleus;

Energetics

I. Enthalpy Change (∆H)
A. Definition of a system
B. Definition of enthalpy (H) and enthalpy change (∆H)
1. Constant pressure process
a) Work done by a system
C. Standard enthalpy change of formation (∆H
f
o)
1. Definition of ∆H
f
o
a) Standard enthalpy change (∆Ho)
b) Standard enthalpy change of formation (∆H
f
o)
c) Standard enthalpy change of formation of an element
2. Direct determination of ∆H
f
o
a) Use of simple calorimeter
D. Other enthalpy change (∆H)
1. Examples of enthalpy change
a) Enthalpy of combustion
b) Enthalpy of atomization
c) Enthalpy of neutralization
d) Enthalpy of hydrogenation
e) Enthalpy of solution
f) Enthalpy of reaction
E. Hess’s Law
1. Indirect determination of ∆H
f
o
a) Hess’s Law
(1) Use of energy level diagram / energy cycle
(2) Use of equation
II. Bonding Energy
A. Bond energy
1. Definition of bond energy
2. Determination of bond energy term (bond enthalpy)
B. Strenght of covalent bond
1. Relationship between bond length and bond energy
2. Factors affecting the bond strength
C. Estimation of enthalpy change by bond energy
III. Energetics of formation of ionic compounds
A. Electron affinity
B. Lattice energy
1. Born-Haber cycle
a) Determination of lattice energy by Born-Haber cycle
2. Factors affecting the value of lattice energy
C. Stoichiometry of ionic compounds
IV. Gibbs free energy change (∆G)
A. Limitation of enthalpy change (∆H)
B. Entropy (S) and entropy change (∆S)
C. Gibbs free energy change (∆G)
I. Enthalpy Change (∆H) Unit 1 Page 1
Topic I. Enthalpy Change (∆H) Unit 1

Reference
Reading
Chemistry in Context, 3rd Edition ELBS pg. 165–166
Physical Chemistry, 4th Edition, Fillans pg. 99 – 101
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 204 – 206
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 146–147

Syllabus
3.0–3.1
Definition of a system
Enthalpy and enthalpy change

Notes
I. Enthalpy Change (∆H)

The discovery of detailed electronic structure of atom serves as a very good example in how does a chemist work.
Nobody have seen the atom directly. The electronic structure is only the result of deduction from some
macroscopic observations (ionization energies and successive ionization energies).

The energy change associated with a reaction provides another useful tools to investigate the chemistry involved.

A. Definition of a system

In the study of energetics, the region or particular quantity of matter of interest is defined as the system. The
surroundings are defined as everything other than the system.




For example, the flask, gas syringe and everything
inside them is defined as the system. The atmosphere
and everything outside the flask and syringe is defined
as the surroundings.



B. Definition of enthalpy (H) and enthalpy change (∆H)

The enthalpy of a substance, sometimes called its heat content, is an indication of the total energy content of the
substance. The absolute enthalpy (H) of a substance depends on

i. potential energy inherent in the electrical and nuclear interactions of the constituent particles (chemical
energy),
ii. kinetic energy possessed by the atoms and sub-atomic particles (kinetic energy)

The absolute enthalpy (H) of a substance is not measurable since it is still not possible to measure all the interaction
between the sub-atomic particles in an atom. Instead, we can measure the enthalpy change (∆H) of a system.

Enthalpy change (∆H) can be arbitrarily defined as the heat change (q) at constant pressure.

I. Enthalpy Change (∆H) Unit 1 Page 2


1. Constant pressure process

Consider the reaction between magnesium and hydrochloric acid :
Mg HCl MgCl H
s aq aq g ( ) ( ) ( ) ( )
+  →  + 2
2 2



Initial stage

Immediate after reaction

Final stage

1. Starting from room temperature (25ºC), we allow
the magnesium and hydrochloric acid to react.










2. Immediately after the reaction, the temperature has
increased due to heat energy released in the
reaction.









3. We let the system cool back to room temperature
(25ºC). We measure all the heat transferred
between system and surroundings in order to return
the system to 25ºC, this is the enthalpy change for
the reaction.


By law of conservation of energy, H
1
and H
2

must be equal. When the system is cooled down
to 25 ºC from 50 ºC, some energy is lost to the
surrounding in form of heat energy(q).

By definition, ∆H = H
final
- H
initial
= H
3
- H
1
= q

Since H
1
is larger than H
3
in this exothermic
reaction, it can be seen that ∆H of an exothermic
reaction is always negative.




Strictly speaking, according to the definition, in order to determine the enthalpy change, the amount of heat
exchanged (q) between the system and the surrounding have to be determined. Since the quantity of the heat
change (q) is difficult to be measured, it would be more convenient if we assume that all the heat energy evolved
in the above example is absorbed by the system. Then the amount of the heat evolved can be calculated from the
heat capacity of the system.

∆H = heat change (q) = - Heat capacity of the system × temperature change of the system (∆T)

N.B. In an exothermic reaction, ∆T is positive but q and ∆H are negative, so a negative sign is added in the
expression.

I. Enthalpy Change (∆H) Unit 1 Page 3


a) Work done by a system

Upon mixing of magnesium and dilute hydrochloric acid in the flask, hydrogen gas evolves. The volume of the
system increase and the system has done a work against the atmospheric pressure.


Work done is defined as

Force(F) × Distance(d)
= [Pressure(P) × Area(A)] × [Volume change(∆V) ÷ Area(A)]
= Pressure(P) × Volume change(∆V)
= P∆V

∆V = V
final
- V
initial

which is positive if the volume of the system is increasing, and
is negative if the volume of the system is decreasing.

If the volume is kept constant in this case, the pressure will no
longer be a constant. More heat will evolve in this reaction since
the work done against atmospheric pressure is now exhibited in
form of heat. Therefore, if the pressure of the system is not kept
constant, according to the definition of ∆H, the heat change (q)
measured would not be the same as the value of ∆H.


Glossary
system surrounding enthalpy change (∆H) heat change / transfer work done

I. Enthalpy Change (∆H) Unit 2 Page 1
Topic I. Enthalpy Change (∆H) Unit 2

Reference
Reading
3.2
Modern Physical Chemistry ELBS pg. 215–222
Chemistry in Context, 3rd Edition ELBS pg. 165 – 169
Physical Chemistry, 4th Edition, Fillans pg. 102 – 104
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 208 – 210
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 148–150

Syllabus
Standard enthalpy change of formation (∆H
f
o)
Determination of enthalpy change
Other enthalpy change

Notes
C. Standard enthalpy change of formation (∆H
f
o)

i. Standard state

For the basis of comparison and tabulation of data, a standard state has been arbitrarily defined.
All the reactants and products
i. in the pure state if they are crystalline substances or liquids
ii. at 1 atmosphere pressure if they are gases
iii. at a concentration of 1M if they are dissolved in a solvent
iv. at a specified temperature, usually, but not necessarily, 298K (25ºC)

The condition of 1 atm and a specified temperature is called standard condition.

ii. Meaning of superscripts

o = standard
º = pure substance
*
= excited electronic state
t = transition state, activated complex

= infinite dilution (with respect to all solutes present)

1. Definition of ∆H
f
o

a) Standard enthalpy change (∆Ho)

The enthalpy change (∆H) for a reaction which occurs under standard conditions is called the standard enthalpy
change. It is represented by the symbol ∆Ho.

Note : The superscript o does not contain the information of the temperature. To be specific, the standard
enthalpy change at 298K should be written as ∆Ho(298K). If the temperature is not specified, by
convention, it is assumed to be 298K.


e.g.
i. 2H
2(g)
+ O
2(g)
→ 2H
2
O
(g)
∆H = -484 kJmol
-1

ii. 2H
2(g)
+ O
2(g)
→ 2H
2
O
(l)
∆H = -572 kJmol
-1


It can be seen that the value of enthalpy change depends
on the physical state of the reactant and product.
Therefore, in writing of equation, the physical state of
individual species must be specified.

I. Enthalpy Change (∆H) Unit 2 Page 2


b) Standard enthalpy change of formation (∆H
f
o)

Standard enthalpy change of formation (∆H
f
o)– The enthalpy change which occurs when 1 mole of a compound is
formed, under standard conditions, from its elements in their
standard state.
e.g.

i. Standard enthalpy of formation of carbon dioxide
C
(graphite)
+ O
2(g)
→ CO
2(g)
∆H
f
o(298K) = -393.5 kJmol
-1


ii. Standard enthalpy of formation of ethane
2C
(graphite)
+ 2H
2(g)
→ C
2
H
4(g)
∆H
f
o(298K) = -52.3 kJmol
-1


Standard enthalpy of formation give us a rough ideal on the energetic stability of the compound respect to its
constituent elements. A more negative standard enthalpy formation means more energetically stable.

c) Standard enthalpy change of formation of an element

According to the definition, standard enthalpy change of formation of an element, e.g. oxygen, is the enthalpy
change associated with the following change, O
2(g)
→ O
2(g)
. Actually, there is no change, the standard enthalpy
change of formation of an element is always zero.


2. Direct determination of ∆H
f
o

Some of the enthalpy of formation can be determined directly by measuring the heat change in direct synthesis of
the compound, e.g. ∆H
f
o[CO
2(g)
], ∆H
f
o[SO
2(g)
].


a) Use of simple calorimeter

A simple calorimeter can be used to determine the amount of heat absorbed or released in a reaction.




For an exothermic reaction, the temperature will raise. For an endothermic reaction, the temperature will fall. If
the heat capacity of the system is known. The heat energy evolved or absorbed can be calculated from the
temperature change.
I. Enthalpy Change (∆H) Unit 2 Page 3


e.g. Determination of enthalpy of reaction of Zn
(s)
+ 2Ag
+
(aq)
→ Zn
2+
+ 2Ag
(s)


An excess of zinc powder was added to 50.0 cm
3
of 0.100M AgNO
3(aq)
in a polystyrene cup. Initially, the
temperature was 21.10ºC and it rose to 25.40ºC. Calculate the enthalpy change for the reaction :

Zn
(s)
+ 2Ag
+
(aq)
→ Zn
2+
+ 2Ag
(s)


Assume that the density of the solution is 1.00 gcm
-3
and its specific heat capacity is 4.18 kJkg
-1
K
-1
. Ignore the
heat capacity of the metals.

i. Since the polystyrene cup is an insulator, its heat capacity is assumed to be zero and there is no energy
exchanged between system and surroundings.

ii. All the chemical energy released in the reactions transformed into heat energy which raises the temperature of
the solution.

iii. As there is no lost of energy to the surroundings, the total energy change in the system is zero.
∆H, due to reaction (at constant T) + change in heat energy of solution = 0

iv. ∆H + mc
p
∆T = 0 where m is mass of the solution
c
p
is the specific heat capacity of the solution under constant pressure
∆T is the temperature change in K

v. ∴ ∆H = -mc
p
∆T = -
50.0
1000
kg × 4.18 kJkg
-1
K
-1
× 4.30 K = -0.899 kJ

vi. The value -0.899 kJ corresponds to 0.00500 mole of silver ions. In order to obtain the value for 2 mole of
silver ions as specified by the equation,
The enthalpy change using 2 mole of Ag
+
ions = -0.899 kJ ×
2 mole
0.00500 mole
= -360 kJ


vii. Zn
(s)
+ 2Ag
+
(aq)
→ Zn
2+
+ 2Ag
(s)

∆H = -360kJmol
-1


viii. Strictly speaking, ∆H cannot be written as ∆Ho in
this question because the conditions of the
experiment were not standard, but the values of ∆H
and ∆Ho would be very close.

ix. Usually, a graph is plotted and extrapolated to
determined the change in temperature, ∆T.

I. Enthalpy Change (∆H) Unit 2 Page 4


D. Other standard enthalpy change (∆Ho)

1. Examples of enthalpy change

a) Standard enthalpy of combustion ∆H
c
o
It refers to the complete combustion of 1 mole of the substance under standard conditions.
e.g. C
(graphite)
+ O
2(g)
→ CO
2(g)
∆H
c
o[C
(graphite)
] = -393.5 kJmol
-1


b) Standard enthalpy of atomization ∆Ho
at

It refers to the formation of 1 mole of gaseous atoms from the element in the defined physical state under
standard conditions.
e.g.
i. C
(graphite)
→ C
(g)
∆Ho
at
[C
(graphite)
]= +715 kJmol
-1

ii. ½H
2(g)
→ H
(g)
∆Ho
at
[½H
2(g)
]= +218 kJmol
-1


For a compound, the value would be the enthalpy change involved in atomization of 1 mole of the compound being
concerned.
e.g. CO
2(g)
→ C
(g)
+ 2O
(g)
∆Ho
at
[CO
2(g)
] = +1606 kJmol
-1


c) Standard enthalpy of neutralization ∆Ho
neutralization

It is the heat change when an acid and a base react to form 1 mole of water under standard condition.
e.g. HCl
(aq)
+ NaOH
(aq)
→ NaCl
(aq)
+ H
2
O
(l)
∆Ho
neutralization
= -57.1 kJmol
-1

CH
3
COOH
(aq)
+ NaOH
(aq)
→ CH
3
COONa
(aq)
+ H
2
O
(l)
∆Ho
neutralization
= -55.2 kJmol
-1

Neutralization of a weak acid is found to be less exothermic than that of a strong acid because energy is required to
ionize the molecules of weak acid first.


d) Standard enthalpy of hydrogenation ∆Ho
hydro

It is the heat change when 1 mole of an unsaturated compound is converted to saturated compound by reaction with
gaseous hydrogen at 1 atm.
e.g. CH
2
CH=CHCH
2(g)
+ 2H
2(g)
→ CH
3
CH
2
CH
2
CH
3(g)
∆Ho
hydro
= -238.8 kJmol
-1


e) Standard enthalpy of solution ∆Ho
sol’n

It is the heat change when 1 mole of a substance is dissolved at 1 atm in a stated amount of solvent or infinite
amount of solvent.
e.g.
i. LiCl 100H O LiCl
(s) 2 (l) (aq,100H O)
2
+ →  ∆Ho
sol’n
= -35 kJmol
-1

ii. LiCl LiCl
s
H O
aq
l
( ) ( )
( ) 2
 →  ∆Ho
sol’n
= -37.2 kJmol
-1


f) Standard enthalpy of reaction ∆Ho
rxn

It is the heat change in a reaction at 1 atm between the number of moles of reactants shown in the equation for the
reaction.
e.g. 2Al
(s)
+ Fe
2
O
3
(s) → 2Fe
(s)
+ Al
2
O
3(s)
∆Ho
rxn
= -845.6 kJmol
-1


Glossary
standard enthalpy of formation standard state calorimeter enthalpy of combustion
enthalpy of atomization enthalpy of neutralization

I. Enthalpy Change (∆H) Unit 2 Page 5

Past Paper
Question
91 2A 1 b ii
92 2A 1 b i
99 1B 7 b

91 2A 1 b ii
1b ii The enthalpy of neutralization of ethanoic acid with aqueous sodium hydroxide is -55.2 kJ mol
-1
while that of
hydrochloric acid is -57.3 kJ mol
-1
. Account for the difference in these two values.
2
The enthalpy of neutralization of a strong acid (HCl) by a strong base (NaOH) is -57.3 kJ mol
-1
. The enthalpy of
neutralization of ethanoic acid with NaOH is -55.2 kJ mol
-1
because ethanoic acid is a weak acid and is only
slightly ionized, and the difference is due to the enthalpy of ionization. 2 marks


92 2A 1 b i
1b i Define the standard enthalpy of formation of a compound, using CH
3
OH
(l)
as an illustration. 1
The standard enthalpy of formation of a compound is the standard enthalpy change that occurs when one mole of
the compound is made from its constituent elements under standard conditions (298 K and 1 atmospheric
pressure). e.g. C
(s)
+ 2H
2(g)
+ ½O
2(g)
→ CH
3
OH
(l)
1 mark

C i Many candidates did not include temperature and pressure in their definition of standard enthalpy of formation.

99 1B 7 b
7b In an experiment to determine the enthalpy change of neutralization, a polystyrene foam cup was used as a
calorimeter. When a solution of an acid was poured into a solution of an alkali in the calorimeter, the temperature
rise was recorded by a thermometer which also served as a stirrer.
State THREE sources of error in the result obtained in such an experiment.


I. Enthalpy Change (∆H) Unit 3 Page 1
Topic I. Enthalpy Change (∆H) Unit 3

Reference
Reading
3.3
Modern Physical Chemistry ELBS pg. 222–226
Chemistry in Context, 3rd Edition ELBS pg. 170–174
Physical Chemistry, Fillans pg. 62–75
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 210 – 213
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 150–157

Syllabus
Hess’s Law
Applications of Hess’s Law

Notes
E. Hess’s Law

1. Indirect determination of ∆H
f
o

Not ∆H
f
o of all compounds can be determined directly.
This is because
i. Not all compounds can be synthesized directly from its constituent elements at standard state. e.g. CH
4(g)

ii. In some reactions, the extent of the reaction is difficult to control. e.g. NH
3(g)

iii. Presence of side products / side reactions. 4Na
(s)
+ O
2(g)
→ 2Na
2
O
(s)
, 2Na
(s)
+ O
2(g)
→ Na
2
O
2(s)


For the ∆H
f
o of the compound which cannot be determined directly, law of conservation of energy (Hess’s Law)
can be used to determine its value.

a) Hess’s Law

Hess's Law - The change in enthalpy accompanying a chemical reaction is independent of the pathway
between the initial and final states.

The enthalpy change for a reaction is constant and is the sum of enthalpy changes for the intermediate steps.

The standard enthalpy change of the reaction, C
(s)
+ ½O
2(g)
→ CO
(g)
, cannot be determined directly since the extent
of the reaction is difficult to control, inevitably some C
(s)
will remain and some CO
2(g)
will be present.
But, the following 2 data can be determined experimentally by calorimetry,
C
(s)
+ O
2(g)
→ CO
2(g)
∆Ho = -394 kJmol
-1

CO
(g)
+ ½O
2(g)
→ CO
2(g)
∆Ho = -283 kJmol
-1


I. Enthalpy Change (∆H) Unit 3 Page 2


(1) Use of energy level diagram / energy cycle


i. Energy Cycle

By Hess's Law, the heat change accompanying Route 1
should equal to that of Route 2.
∴ ∆H
1
= ∆H
2
+ ∆H
3

∆H
2
= ∆H
1
- ∆H
3

∴ ∆H
f
o[CO
(g)
] = ∆H
2

= -394 kJmol
-1
- (-283 kJmol
-1
)
= -111 kJmol
-1





ii. Energy Level Diagram


To represent the relative enthalpy of the substance
involved, an energy level diagram may be used.

Steps of drawing an energy level diagram
1. Draw a line to represent the enthalpy of 1 mole of
graphite and 1 mole of oxygen at standard
condition.
2. The combustion of 1 mole of graphite produces
CO
2(g)
and releases 394 kJ.
3. The combustion of CO
(g)
gives the same product, 1
mole of CO
2(g)
. The energy released is 283 kJ.
4. The gap represents the heat of formation of CO
(g)
.



Steps of constructing energy cycle / energy level diagram

1. Write down an equation according to the definition of the problem.
2. Write down the common reference to which both reactant and product are related. In the above example, it is
CO
2(g)
.
3. Complete the cycle / diagram.

N.B. In general, there are three popular common reference used in construction of energy cycles.
They are i. combustion products
ii. constituent elements in their standard states
iii. constituent atoms

I. Enthalpy Change (∆H) Unit 3 Page 3


(2) Use of equation

The standard heat of reaction can also be determined if the standard heat of formation of the reactants and products
are given.

The generalized statement of this approach in the calculation of ∆Ho
rxn
is
∆Ho
rxn
= Σ∆H
f
o(products) - Σ∆H
f
o(reactants)

e.g.
C
(s)
+ O
2(g)
→ CO
2(g)
∆H
f
o = -394 kJmol
-1

CO
(g)
+ ½O
2(g)
→ CO
2(g)
∆H
f
o = -283 kJmol
-1


If you want to determine the heat of formation of CO
(g)
, C
(s)
+ ½O
2(g)
→ CO
(g)
, following method may be used.

For the reaction, CO
(g)
+ ½O
2(g)
→ CO
2(g)
, ∆Ho
rxn
= -283 kJmol
-1


∆Ho
rxn
= Σ∆H
f
o(products) - Σ∆H
f
o(reactants)
-283 kJmol
-1
= {∆H
f
o[CO
2(g)
]} - {∆H
f
o[CO
(g)
] + ∆H
f
o[½O
2(g)
]}
-283 kJmol
-1
= (-394 kJmol
-1
) - (∆H
f
o[CO
(g)
] + 0 kJmol
-1
)
∆H
f
o[CO
(g)
] = (-394 kJmol
-1
) - (-283 kJmol
-1
) = -111 kJmol
-1


Note : By definition, ∆H
f
o of any element, e.g. O
2
, is zero.

Or simply, by doing some manipulations on the equations.

C
(s)
+ O
2(g)
→ CO
2(g)
∆H
f
o = -394 kJmol
-1

CO
(g)
+ ½O
2(g)
→ CO
2(g)
∆H
f
o = -283 kJmol
-1


i. Reverse the second equation and the sign of ∆H
f
o.
ii. Add the two equations together.

C
(s)
+ O
2(g)
→ CO
2(g)
∆H
f
o = -394 kJmol
-1

CO
2(g)
→ CO
(g)
+ ½O
2(g)
∆H
f
o = +283 kJmol
-1

---------------------------------------------------------------------------------------------
C
(s)
+ O
2(g)
+ CO
2(g)
→ CO
2(g)
+ CO
(g)
+ ½O
2(g)

---------------------------------------------------------------------------------------------
C
(s)
+ ½O
2(g)
→ CO
(g)
∆H
f
o = -111 kJmol
-1



Glossary
Hess’s Law energy level diagram energy cycle

I. Enthalpy Change (∆H) Unit 3 Page 4

Past Paper
Question
90 1A 2 b
91 1B 4 b i ii iii 91 2A 1 b i
92 2A 1 b ii
93 2A 3 b i ii
94 2A 2 a i ii
95 2A 1 b
97 2A 2 c
98 2A 2 c i ii
90 1A 2 b
2b Show how ∆Ho
f
for CuSO
4
·5H
2
O
(s)
can be determined using the following data:
∆Ho
soln
CuSO
4
·5H
2
O
(s)
= + 8 kJ mol
-1
; ∆Ho
f
CuSO
4(s)
= - 773 kJ mol
-1

∆Ho
soln
CuSO
4(s)
= - 66 kJ mol
-1
; ∆Ho
f
H
2
O
(l)
= - 286 kJ mol
-1

3

aq + Cu
(s)
+ S
(s)
+ 9/2 O
2(g)
+ 5H
2(g)
CuSO
4
?H
2
O
(s)
+ aq
aq + CuSO
4(s)
+ 5H
2
O
(l)
CuSO
4(aq)
+ 5H
2
O
(l)
∆H
f
CuSO
4
?H
2
O
(s)
∆H
f
CuSO
4(s)
+ 5 ? ∆H
f
H
2
O
(l)
∆H
soln
CuSO
4(s)
∆H
soln
CuSO
4
?H
2
O
(s)

Cu
(s)
+ S
(s)
+ 2O
2(g)
→ CuSO
4(s)
- 773 kJ
5H
2(g)
+ 2½O
2(g)
→ 5H
2
O
(l)
5 × - 286 kJ
aq + CuSO
4(s)
→ CuSO
4(aq)
- 66 kJ
CuSO
4(aq)
+ 5H
2
O
(l)
→ CuSO
4
·5H
2
O
(s)
+ aq - 8 kJ
-------------------------------------------------------------------------------------------
Cu
(s)
+ S
(s)
+ 5H
2(g)
+ 4½O
2(g)
→ CuSO
4
·5H
2
O
(s)

∴∆H
f
o for CuSO
4
·5H
2
O
(s)
= (-773) + 5(-286) + (-66) - 8 = -2277 kJ mol
-1

2 marks for working (cycle/equations and expressions)
1 mark for correct answer (sign, numeric and units)
Deduct ½ mark for wrong units.

C Only about half of the candidates did this numerical problem correctly. Many errors arose as a result of a poorly
constructed Born-Haber cycle. Very few candidates used the more analytical approach of setting up equations.


91 1B 4 b i ii iii
4b You are required to determine indirectly the enthalpy of formation of calcium carbonate(s). You are give the
reagents: calcium, calcium carbonate, a strong acid, and water; the enthalpies of formation of carbon dioxide
(g)

and water
(l)
are available.

i Give equations of suitable reactions for this determination. 2
CaCO
3(s)
+ 2HCl
(aq)
→ CaCl
2(aq)
+ CO
2(g)
+ H
2
O
(l)

Ca
(s)
+ 2HCl
(aq)
→ CaCl
2(aq)
+ H
2(g)
2 marks
(missing or incorrect physical state -½; wrong coefficient -½; inappropriate acid e.g. H
2
SO
4
and HNO
3
-½)

ii Name the major pieces of apparatus needed for this determination. 2
Calorimeter (beaker or plastic cup, stirrer, temperature bath, insulation, electric heater) ½ mark
thermometer or thermocouple ½ mark
measuring cylinder, burette or pipette ½ mark
balance ½ mark

iii Suggest one experimental difficulty in the direct determination of the enthalpy of formation of calcium carbonate
from its elements.
2

Ca
(s)
+ C
(s)
+
3
2
O
2(g)
→ CaCO
3(s)

Side reactions: 2Ca
(s)
+ O
2(g)
→ 2CaO
(s)
; C
(s)
+ O
2(g)
→ CO
2(g)

2 marks for any one explanation:
- extent of reaction cannot be controlled
- side reactions
- directly combustion of Ca can be violent
- cannot react or cannot react to form CaCO
3
(1 mark only)

C This section showed that the candidates were weak in applying general chemical knowledge to experiments. Most
candidates scored marks by pointing out a very common piece of equipment and giving a partial explanation of
the experimental difficulty. Of those who gave the equations with correct species, many failed to give balanced
coefficients and states of the species. Many incorrect explanations like "heat loss to surroundings" and "large heat
of formation" were given for (iii).

I. Enthalpy Change (∆H) Unit 3 Page 5
91 2A 1 b ii
1b i Calculate the enthalpy of formation of NaCl
(s)
from the following data :
Reaction ∆Ho/kJmol
-1

NaOH
(aq)
+ HCl
(aq)
→ NaCl
(aq)
+ H
2
O
(l)
-57.3
H
2(g)
+ ½O
2(g)
→ H
2
O
(l)
-285.9
½H
2(g)
+ ½Cl
2(g)
→ HCl
(g)
-92.3
HCl
(g)
+ aq → HCl
(aq)
-71.9
Na
(s)
+ ½O
2(g)
+ ½H
2(g)
+ aq → NaOH
(aq)
-425.6
NaCl
(s)
+ aq → NaCl
(aq)
+3.9
4
Na
(s)
+ ½O
2(g)
+ ½H
2(g)
+ aq → NaOH
(aq)
∆Ho = -425.6 kJ mol
-1

NaOH
(aq)
+ HCl
(aq)
→ NaCl
(aq)
+ H
2
O
(l)
∆Ho = -57.3 kJ mol
-1

H
2
O
(l)
→ H
2(g)
+ ½O
2(g)
∆Ho = +285.9 kJ mol
-1

½H
2(g)
+ ½Cl
2(g)
→ HCl
(aq)
∆Ho = -92.3 + (-71.9) = -164.2 kJ mol
-1

NaCl
(aq)
→ NaCl
(s)
+ aq ∆Ho = -3.9 kJ mol
-1
1 mark
∆Ho = (-425.6) + (-57.3) + (+285.9) + (-164.2) + (-3.9) = -365.1 kJ mol
-1
(no unit -½) 3 marks

C Some candidates were not able to give a correct energy cycle and hence failed to obtain the correct answer.
Some weaker candidates did not even give state symbols in the chemical equations.


92 2A 1 b ii
1b ii Given the following thermochemical data at 298K :
Standard enthalpy of combustion of CH
3
OH
(l)
-726.6 kJmol
-1

Standard enthalpy of formation of CO
2(g)
-393.5 kJmol
-1

Standard enthalpy of formation of H
2
O
(l)
-285.8 kJmol
-1

Calculate the standard enthalpy of formation of CH
3
OH
(l)
at 298K.
3

CH
3
OH
(l)
+
3
2
O
2(g)
→ CO
2(g)
+ 2H
2
O
(l)
∆Ho = -726.6 kJmol
-1

∆Ho = Σn
p
(∆H
f
o)
p
- Σn
r
(∆H
f
o)
r

∆Ho = (∆H
f
o(CO
2
) + 2∆H
f
o(H
2
O) - (∆H
f
o(CH
3
OH) +
3
2
∆H
f
o(O
2
))
Since ∆H
f
o(O
2
) is zero.
∴ -726.6 = (-393.5 + 2 × (-285.8)) - (∆H
f
o(CH
3
OH) + 0) correct steps 2 marks
∴ ∆H
f
o(CH
3
OH) = -238.5 kJ mol
-1
missing sign(-1), missing unit(-½) correct answer 1 mark


93 2A 3 b i ii
3b Given the following thermochemical data at 298 K:
Compound

H
o
combustion
/kJ mol
-1

H
o
formation
/kJ mol
-1
cyclopropane (g) -2091 —
propene (g) -2058 —
propane (g) -2220 —
water (l) — -285.8


i Calculate the enthalpy change involved in the hydrogenation of cyclopropane to propane. 4

(1) ∆
(g)
+
9
2
O
2(g)
→ 3H
2
O
(l)
+ 3CO
2(g)
∆H = -2091 kJmol
-1

(2) CH
3
CH
2
CH
3(g)
+ 5O
2(g)
→ 4H
2
O
(l)
+ 3CO
2(g)
∆H = -2220 kJmol
-1

(3) H
2(g)
+ ½O
2(g)
→ H
2
O
(l)
∆H = -285.8 kJmol
-1
1 mark
(1) + (3) - (2)

(g)
+ H
2(g)
→ CH
3
CH
2
CH
3(g)
1 mark
∆H = -2091 + (-285.8) - (-2220) = -156.8 kJmol
-1
2 marks

ii Calculate the enthalpy change involved in the conversion of cyclopropane to propene. Comment on the relative
stabilities of cyclopropane and propene.
4

(4) H
2
C=CH–CH
3(g)
+
9
2
O
2(g)
→ 3CO
2(g)
+ 3H
2
O
(l)
∆H = -2058 kJmol
-1

(1) - (4) ∆
(g)
→ H
2
C=CH–CH
3(g)
1 mark
∆H = -2091 - (-2058) = -33 kJmol
-1
1 mark
The conversion from cyclopropane to propene is exothermic, hence propene is more stable 1 mark
because in the structure of cyclopropane there is squeezing of bond angles / ring is highly strained / poor
overlapping of atomic orbital. 1 mark

C Weaker candidates produced wrong answers because they used the wrong signs and some could not correlate the
fact that the cyclopropane molecule was highly strained, and that it would release the excess energy upon
conversion to propene, resulting in an exothermic reaction.


I. Enthalpy Change (∆H) Unit 3 Page 6
94 2A 2 a i ii
2a Given the following thermochemical data.
Reaction ∆Ho
298
/ kJ mol
-1

C (graphite) + 2H
2(g)
→ CH
4(g)
- 75.0
C (graphite) + O
2(g)
→ CO
2(g)
- 393.5
H
2(g)
+ ½O
2(g)
→H
2
O
(l)
- 285.9

i Calculate the enthalpy change ∆Ho
298
for the reaction CH
4(g)
+ 2O
2(g)
→ 2H
2
O
(l)
+ CO
2(g)
. 2
∆Ho
298
= -393.5 + 2(-285.9) - (-75.0) = - 890.3 kJmol
-1
2 marks
ii The enthalpy change ∆Ho
298
is - 801.7 kJ mol
-1
for the following reaction.
CH
4(g)
+ 2O
2(g)
→ 2H
2
O
(g)
+ CO
2(g)

Calculate the enthalpy change of vaporization of water at 298K.
2
CH
4(g)
+ 2O
2(g)
→ 2H
2
O
(g)
+ CO
2(g)
∆H = - 801.7 kJ mol
-1

- CH
4(g)
+ 2O
2(g)
→ 2H
2
O
(l)
+ CO
2(g)
∆H = - 890.3 kJ mol
-1

––––––––––––––––––––––––––––––––––––––––––––––––––––––
2H
2
O
(l)
→ 2H
2
O
(g)
∆H = + 88.6 kJ mol
-1
1 mark
∆Ho
vaporization
(H
2
O) = + 44.3 kJ mol
-1
1 mark

C Many candidates gave +88.6 kJ, instead of + 44.3 kJ mol
-1
for the enthalpy change of vaporization of water.

95 2A 1 b
1b You are provided with the following thermochemical data:
Reaction ∆Ho
298
/kJmol
-1

Ag
(s)
+ aq → Ag
+
(aq)
+ e
-
+105.56
1
2
N
2(g)
+
3
2
O
2(g)
+ aq + e
-
→ NO
3
-
(aq)
-207.36
1
2
Cl
2(g)
+ aq + e
-
→ Cl
-
(aq)
-167.15
Ag
(s)
+
1
2
Cl
2(g)
→ AgCl
(s)
-127.07
Calculate the standard enthalpy change for the reaction
AgNO
3(aq)
+ HCl
(aq)
→ AgCl
(s)
+ HNO
3(aq)
.
4
The reaction AgNO
3(aq)
+ HCl
(aq)
→ AgCl
(s)
+ HNO
3(aq)
is equivalent to Ag
+
(aq)
+ Cl
-
(aq)
→ AgCl
(s)
1 mark
∆H = Σ∆H
f
(products) - Σ∆H
f
(reactants) 1 mark
= -127.07 - (+105.56) - (-167.15)
= -65.48 kJmol
-1
2 mark
(Accept any correct method using an energy cycle.)

C Some candidates could not construct the energy cycle correctly. Mistakes in the numerical calculation were
common.


97 2A 2 c
2c Given the following thermochemical data at 298 K:
Standard enthalpy change of formation of CO
2(g)
= -393.5 kJ mol
-1

Standard enthalpy change of formation of H
2
O
(l)
= -285.8 kJ mol
-1

Standard enthalpy change of combustion of CH
3
CH
2
OH
(l)
= -1336.9 kJ mol
-1

calculate the standard enthalpy change of formation of CH
3
CH
2
OH
(l)
at 298 K.
4

I. Enthalpy Change (∆H) Unit 3 Page 7
98 2A 2 c i ii
2c Both H
2(g)
and CH
3
OH
(l)
are possible fuels for powering rockets. Their combustion reactions are shown below.

H
2(g)
+ ½O
2(g)
→ H
2
O
(g)

CH
3
OH
(l)
+ 1½O
2(g)
→ CO
2(g)
+ 2H
2
O
(g)


Compound molar mass / g ∆H
f
o / kJmol
-1

CO
2(g)
44 -394
H
2
O
(g)
18 -242
CH
3
OH
(l)
32 -239

i For each of the above reactions, calculate the enthalpy change at 298 K per kg of the fuel-oxygen mixture in the
mole ratio as indicated in the stoichiometric equation

ii The effectiveness of a fuel can be estimated by dividing the enthalpy change per kg of the fuel-oxygen mixture in
its combustion reaction by the average molar mass of the product(s) in g.
Deduce which of the above two fuels is more effective in powering rockets.


II. Bonding Energy Unit 1 Page 1
Topic II. Bonding Energy Unit 1

Reference
Reading
3.4.1
Modern Physical Chemistry ELBS pg. 229–233
Chemistry in Context, 3rd Edition ELBS pg. 174–180
Physical Chemistry, Fillans pg. 76–83
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 214 – 215
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 157–159

Syllabus
Definition of bond enthalpies
Determination of bond enthalpies

Notes
II. Bonding Energy

This is the principles of energetics and bonding energy again.

i. Energy change always involves with bond formation and bond breaking. Usually, the bond formation process
evolves energy, i.e. exothermic and bond breaking process absorbs energy, i.e. endothermic.
ii. Bonding is just a balance between attractions and repulsions. If the attractions between atoms are stronger
that the repulsions, the bond will form. Otherwise, the bond will be weak or will not form at all.

A. Bond energy

1. Definition of bond energy

In discussion of bond energy, two definitions have to be made clear.

Bond Dissociation Energy, D: The energy required to break one mole of a particular covalent bonds in
molecules. e.g. Cl–Cl bond in Cl
2
molecule
In contract, enthalpy of atomization is the energy required to produce one
mole of gaseous atom, for a diatomic molecule, it is half of D.

Bond Energy Terms, E(X–Y): Also known as average bond energy or bond enthalpy, is an average value of
bond dissociation energies for a given type of bond. e.g. E(C–H) is the average
value of bond dissociation energies of C-H bond in all kinds of hydrocarbon.


2 1
C C
H H
H H
H OH

Not all C–H bonds are equivalent, even in the same
molecule. For example, C–H bond at position 1 is
stronger than the bond at position 2. The presence of
the electronegative oxygen makes the C–H bonds
become more polar and stronger.


By convention, if not specified, bond energy is referring to bond energy term (average bond energy).

Enthalpy changes for four successive dissociation reactions :

Reaction ∆Ho(298K) kJmol
-1

CH
4(g)
→ CH
3(g)
+ H
(g)
+425
CH
3(g)
→ CH
2(g)
+ H
(g)
+470
CH
2(g)
→ CH
(g)
+ H
(g)
+416
CH
(g)
→ C
(g)
+ H
(g)
+335

Since dissociation energy refers to a particular bond, it is important to specify the process involved.
The standard enthalpy change for the reaction, CH
4(g)
→ C
(g)
+ 4H
(g)
, ∆Ho
at
[CH
4(g)
]
= (+425) + (+470) + (416) + (+335) = +1646 kJmol
-1


The bond energy terms, E(C–H), in CH
4(g)
= +1646 kJmol
-1
÷ 4 = 413 kJmol
-1


In contrast with the bond dissociation energy, bond energy term does not refer to one particular bond but it is the
average bond energy of a particular type of bond.
II. Bonding Energy Unit 1 Page 2


After the collection of a number of bond dissociation
energies for a particular type of bond, the bond energy
term can be determined.

Bond E(X-Y) kJmol
-1

C–H 413
C–C 347
C–Cl 346





2. Determination of bond energy term (bond enthalpy)

Bond energy term can be determined by i. thermochemical methods (by Hess’s Law)
ii. spectroscopic methods (not required)
iii. electron impact methods (not required)

Determination of E(C=O) in CO
2
by using an energy level diagram

E(C=O) should be half of the enthalpy of reaction of CO
2(g)
→ C
(g)
+ 2O
(g)
, ∆Ho
at
[CO
2(g)
]


The enthalpy changes of the first three stages can be determined
experimentally.

Stage 1 Atomization of graphite
C
(graphite)
→ C
(g)
∆Ho
at
[C
(graphite)
] = +715 kJmol
-1


Stage 2 Atomization of oxygen
O
2(g)
→ 2O
(g)
∆Ho
at
[O
2(g)
] = +498 kJmol
-1


Stage 3 Enthalpy of formation of carbon dioxide
C
(graphite)
+ O
2(g)
→ CO
2(g)
∆H
f
o[CO
2(g)
] = -393 kJmol
-1


Stage 4 Enthalpy of atomization of carbon dioxide
CO
2(g)
→ C
(g)
+ 2O
(g)
∆Ho
at
[CO
2(g)
]

By Hess’s Law
∆Ho
at
[CO
2(g)
] = - ∆H
f
o[CO
2(g)
] + ∆Ho
at
[C
(graphite)
] + ∆Ho
atm
[O
2(g)
]
= - (-393 kJmol
-1
) + 715 kJmol
-1
+ 498 kJmol
-1

= +1606 kJmol
-1



E(C=O) = ∆Ho
at
[CO
2(g)
] ÷ 2 = +1606 kJmol
-1
÷ 2 = +803 kJmol
-1


Glossary
bond energy bond energy terms (average bond energy) bond dissociation energy
enthalpy of atomization


Past Paper
Question




II. Bonding Energy Unit 2 Page 1
Topic II. Bonding Energy Unit 2

Reference
Reading
3.4.2–3.4.3
Modern Physical Chemistry ELBS pg. 229–233
Chemistry in Context, 3rd Edition ELBS pg. 174–180
Physical Chemistry, Fillans pg. 76–83
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg.

Syllabus
Strength of covalent bond
Factors affecting the bond strength

Notes
B. Strength of covalent bond

1. Relationship between bond length and bond energy

The bond strength of a bond can be measured by the bond energy. The stronger the bond, the more energy will be
required to break the bond.

For identical atoms, the bond strength is inversely proportional to the bond length. The stronger the bond, the
closer will be the nuclei drawn together. Therefore, bond strength can be served as a indicator of bond strength.

Bond Bond length / nm Bond energy
C–C 0.154 +347 kJmol
-1

C=C 0.134 +612 kJmol
-1


2. Factors affecting the bond strength

i. atomic size
ii. number of bonding electrons / bond order
iii. bond polarity

i. atomic size

Bond Bond length/nm Bond energy
F–F 0.142 +158 kJmol
-1

Cl–Cl 0.199 +242 kJmol
-1

Br–Br 0.228 +193 kJmol
-1

I–I 0.266 +151 kJmol
-1





Bond Bond length/nm Bond energy
F–H 0.092 +568 kJmol
-1

Cl–H 0.127 +432 kJmol
-1

Br–H 0.141 +366 kJmol
-1

I–H 0.161 +298 kJmol
-1

As the size of the atoms gets bigger, the bonding
electrons are further from the nucleus and the shielding
effect of the electron is getting more significant.
Therefore, the strength of the bond decreases with
increasing atomic size.
Fluorine shows anomaly in group VII, this is because of
the repulsion between lone pairs on the two atoms
which weakens the bond.

However if F is bonded to an atom with no lone pair,
owing to the small size of F, the bond would be very
strong. This explains why F four a larger variety of
compounds that the other elements because the
compound formed is energetically more stable than the
others.


ii. number of bonding electrons / bond order

Bond Bond energy / kJmol
-1

C–C +346
C=C +610
C≡C +837
N–N +163
N=N +410
N≡N +945
For the same kind of bond, e.g. C–C bond, the bond
energy increases with increasing no. of bonding
electron.
II. Bonding Energy Unit 2 Page 2


iii. bond polarity

Bond Difference in E.N. Bond energy
N–H 0.9 +388
O–H 1.4 +463
F–H 1.9 +562
Polarization of the bond gives the bond certain ionic
character. The gives the bond certain ionic attraction on
top of covalent bond.

Glossary
bond length bond order molecular orbital theory bond polarity

Past Paper
Question
90 2B 4 c
91 2B 4 c i
95 2B 4 a ii 95 2B 4 c I
98 1A 1 b ii

90 2B 4 c
4 Account for the following observations.
4c Dinitrogen tetraoxide and hydrogen peroxide are both unstable to heat. 3
N
2
O
4
d 2NO
2

H
2
O
2
→ 2HO· or homolytic bond fission/state the products 1 mark
weak N–N and O–O bond strengths 1 mark
due to lone pair-lone pair repulsions in O
2
and long N–N bond in N
2
1 mark


91 2B 4 c i
4c i Why is the Cl-Cl bond stronger than the F-F or Br-Br bonds? 2
We expect that the X-X bond energy decreases on descending the group because the distance between the nuclear
protons and the bond-pair electron increases, so the attractive force decreases. This is so for Cl
2
and Br
2
.
1 mark
The F-F bond is weaker than that of Cl
2
due to non-bonding electron repulsion between lone pairs, on the F nuclei.
1 mark

C i The abnormally weak F–F bond strength was attributed to 'internuclear repulsion', to 'the small size of the fluorine
atom', or to 'electron repulsion' and 'lone-pair repulsion', and few answers cited non-bonding electron repulsion
between the two fluorine atoms. Some candidates thought that the Cl–Cl bond is stronger than the Br–Br bond
because 'chlorine is more electronegative' or because 'the effective nuclear charge of Br is smaller'. Two points
were required for the second part of the answer : a mention of the change in distance between nuclear protons and
shared (bond-pair) electrons, and the consequent change in attractive force.


95 2B 4 a ii
4a Explain the following facts:
ii The bond dissociation energy of F
2
is less than that of Cl
2
. 2
Unusually short F–F distance leads to high repulsion due to lone pair electrons of fluorine atoms. Therefore F–F
bond is weaker than expected. 2 marks

C Many candidates did not know that the small bond dissociation energy of F
2
is due to the strong repulsion of lone
electron pairs of the fluorine atoms in the F
2
molecule.


95 2B 4 c i
4c Consider the data given below for the hydrogen halides and answer the questions that follow.
Standard enthalpy change of formation / kJmol
-1
Bond dissociation energy / kJmol
-1

H–F -269.4 +562
H–Cl -92.8 +430
H–Br -36.8 +367
H–I +26.1 +298

i Explain briefly the trend in the bond dissociation energy of the hydrogen halides. 3
Trend : Bond dissociation energy decreases with increasing molecular mass of hydrogen halides. 1 mark
Explanation : The H–X bond lengths increase as the atomic radii of the halogens increase. The longer the
bond, the weaker it is and the bond dissociation energy is smaller. 2 marks

C Some candidates did not know that the H–X bond lengths increase as the atomic radii of the halogens increase
from F to I and that the longer the bond, the weaker it is and the smaller is the bond dissociation energy.


98 1A 1 b ii
1b ii Explain why the carbon-oxygen bond lengths in CO and CO
2
are different. 2

II. Bonding Energy Unit 3 Page 1
Topic II. Bonding Energy Unit 3

Reference
Reading
3.4.4
Modern Physical Chemistry ELBS pg. 229–233
Chemistry in Context, 3rd Edition ELBS pg. 174–180
Physical Chemistry, Fillans pg. 76–83
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 157–158

Syllabus
Estimation of bond enthalpies and bond length

Notes
C. Estimation of enthalpy change by bond energy

With the atomization energies and Hess's Law, bond energy terms can be used for estimation of enthalpy changes.

Since energy is required in bond breaking and energy is released in bond formation, the overall enthalpy can be
estimated by the equation, ∆H = energy required - energy released = ΣE(bond broken) - ΣE(bond formed).

i. Estimation of Enthalpy of formation of methane, CH
4(g)


Value estimation by bond energy terms


E(C–H) +413 kJmol
-1

∆Ho
at
[C
(graphite)
] +715 kJmol
-1
∆Ho
at
[½H
2(g)
] +218 kJmol
-1


∆H
f
o[CH
4(g)
]
= energy required - energy released
= (∆Ho
at
[C
(graphite)
] + 4 × ∆Ho
at
[½H
2(g)
]) - (4 × E(C–H))
= (715 + 4 × 218) - (4 × 413)
= -65 kJmol
-1



Value determination by Hess’s Law


∆H
c
o[C
(graphite)
] -393.5 kJmol
-1

∆H
c
o[H
2(g)
] -285.8 kJmol
-1

∆H
c
o[CH
4(g)
] -890.3 kJmol
-1


∆H
f
o[CH
4(g)
]
= (∆H
c
o[C
(graphite)
] + 2 × ∆H
c
o[H
2(g)
]) - ∆H
c
o[CH
4(g)
]
= (-393.5 + 2 × (-285.8)) - (-890.3)
= -74.8 kJmol
-1




It can be seen that the value estimated by bond energy terms differs from the value determined by Hess’s Law.
This is because bond energy terms is only the average bond energy and not the actual value of the bond being
concerned. Therefore, the value from Hess’s Law is always preferred.

II. Bonding Energy Unit 3 Page 2


ii. Estimation of Enthalpy of formation of 1-chloroethane, CH
3
CH
2
Cl
(g)
, by bond energy terms



E(C–H) +413 kJmol
-1

E(C–C) +347 kJmol
-1

E(C–Cl) +346 kJmol
-1

∆Ho
at
[C
(graphite)
] +715 kJmol
-1

∆Ho
at
[½H
2(g)
] +218 kJmol
-1

∆Ho
at
[½Cl
2(g)
] +122 kJmol
-1




∆H
f
o[CH
3
CH
2
Cl
(g)
]
= energy required - energy released
= (2 × ∆Ho
at
[C
(graphite)
] + 5 × ∆Ho
at
[½H
2(g)
] + ∆Ho
at
[½Cl
2(g)
]) - (5 × E(C–H) + E(C–C) + E(C–Cl))
= (2 × 715 + 5 × 218 + 122) - (5 × 413 + 347 + 346)
= -116 kJmol
-1




iii. Use of bond energy term to predict the heat of reaction

For the reaction, H–H(g) + Cl–Cl(g) → 2H–Cl(g)


E(H–H) +435.9 kJmol
-1

E(Cl–Cl) +243.4 kJmol
-1

E(H–Cl) +432.0 kJmol
-1


∆H = energy required - energy released
= ΣE(bond broken) - ΣE(bond formed)
= (E(H–H) + E(Cl–Cl)) - (2 × E(H–Cl))
= (435.9 + 243.4) - (2 × 432.0)
= -184.7 kJmol
-1
(experimental value 184.6 kJmol
-1
)


Glossary


Past Paper
Question
96 2A 1 a i

96 2A 1 a i ii
1a For the hydrogenation of buta-1,3-diene,
H
2
C=CH–CH=CH
2(g)
+ 2H
2(g)
→ CH
3
CH
2
CH
2
CH
3(g)

the experimental molar enthalpy change is -239 kJmol
-1
.

i Estimate the molar enthalpy change for the above hydrogenation using the bond energy terms below :
Bond Bond energy term / kJmol
-1

H–H 436
C–H 413
C–C 346
C=C 611
2
∆H = -2E
C–C
- 4E
C–H
+ 2E
C–C
+ 2E
H–H
1 mark
or = -2(346) - 4(413) + 2(611) + 2(436) (1 mark)
= -250 kJmol
-1
1 mark
(0 marks for omitting the eve sign; deduct ½ mark for no units)


III. Energetics of formation of ionic compounds Page 1
Topic III. Energetics of formation of ionic compounds

Reference
Reading
3.5.1–3.5.2
Modern Physical Chemistry ELBS pg. 69–70, 74, 226–228
Chemistry in Context, 3rd Edition ELBS pg. 180–182
Physical Chemistry, Fillans pg. 84–90
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 216 – 218
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 85–86, 160–162

Syllabus
Lattice energy
Electron affinity and magnitude of electron affinity
Determination of lattice energy by Born-Haber cycle

Notes
III. Energetics of formation of ionic compounds

A. Electron affinity

Electron affinity, ∆H
e
o or EA – the enthalpy change which occurs when one mole of electrons are added to one
mole of neutral atom in the gaseous state to form one mole of gaseous ions
under standard conditions.,
i.e. A
(g)
+ e
-
→ A
-
(g)
.

The value of the electron affinity is depending on the attraction between the incoming electron and the nucleus and
the shielding effect offered by the existing electrons.

i.e. the electron affinity of O,
O
(g)
+ e
-
→ O
-
(g)
∆H
e
o = -142 kJmol
-1


i.e. the electron affinity of O
-
(or second electron affinity of O)
O
-
(g)
+ e
-
→ O
2-
(g)
∆H
e
o = +791 kJmol
-1


The first EA of O is exothermic because the attraction between the incoming electron and the nucleus is atronger
than the repulsion between the incoming electron and the existing electrons.
The second EA of O is endothermic because in the presence of the extra electron, the extra electron charge will
offer a stronger repulsion with the incoming electron. Furthermore, the electron cloud of O
-
will expand and the
incoming electron will occupy a position further from the nucleus which weakens the attraction with the nucleus.



B. Lattice energy

Lattice energy, ∆Ho
lat
– the enthalpy change which occurs when one mole of the ionic compound is formed, as a
crystal lattice, from its constituent gaseous ions.
The value of lattice energy is directly proportional to the strength of the ionic bond.

e.g. Na
+
(g)
+ Cl
-
(g)
→ NaCl
(s)
∆Ho
lat
= -788.5 kJmol
-1


Since lattice energy always associates with bond formation, it must have a negative value, i.e. exothermic.

The lattice energy cannot be determined directly by experiment, we construct an energy diagram called Born-
Haber cycle to determine the lattice energy.

1. Born-Haber cycle

Born-Harber cycle – A thermodynamic cycle derived by application of Hess’s Law. Commonly used to calculate
lattice energies of ionic solids and average bond energies of covalent compound.



III. Energetics of formation of ionic compounds Page 2


a) Determination of lattice energy by Born-Haber cycle


Generalized Born-Haber cycle for an ionic
compound


Transformation of elements in their standard states
to gaseous ions, ∆H
1

∆Ho
at
[Na
(s)
] = +108 kJmol
-1

∆H
i
o[Na
(g)
] = +500 kJmol
-1

∆Ho
at
[½Cl
2(g)
] = +121 kJmol
-1
∆H
e
o[Cl
(g)
] = -364 kJmol
-1

∆H
1
= ∆Ho
at
[Na
(s)
] + ∆H
i
o[Na
(g)
] + ∆Ho
at
[½Cl
2(g)
]
+ ∆H
e
o[Cl
(g)
]
= 108 + 500 + 121 + (-364)
= 365 kJmol
-1


Standard heat of formation of the ionic crystal
lattice, ∆H
2
∆H
2
= ∆Ho
f
[NaCl
(s)
] = -411 kJmol
-1


Lattice energy, ∆Ho
lat
= ∆Ho
lat
[NaCl
(s)
]

Finally, by Hess’s Law
∆H
1
+ ∆Ho
lat
[NaCl
(s)
] = ∆H
2
∆Ho
lat
[NaCl
(s)
] = ∆H
2
− ∆H
1

= (-411) - (+365)
= -776 kJmol
-1

Detail Born Haber cycle of sodium chloride

Note: ∆H
i
o – ionization energy, I.E.
∆H
e
o – electron affinity, E.A.


3. Factors affecting the value of lattice energy

The magnitude of the lattice energy depends on
i. The packing efficiency of the crystal lattice
– small and similarity in size of ions result in better packing and more negative lattice energy
ii. The charge density of the constituent ions
– higher the charge density of the ion, stronger will be the electrostatic attraction and the lattice energy will
be more negative.

Lattice energy ∝
1
r
+
+ r
-
r
+
, r
-
: radii of cation and anion



III. Energetics of formation of ionic compounds Page 3


C. Stoichiometry of ionic compounds

The calculation of the lattice energies and use of Born-Haber cycle can also be used to explain why group I, II and
III metal always form M
+
, M
2+
and M
3+
ion respectively.

e.g. Born-Haber cycle for Ca
+
Cl
-
, Ca
2+
(Cl
-
)
2
and Ca
3+
(Cl
-
)
3


The lattice energies are calculated based on the mathematical model.

By summing up the terms, the enthalpy of formation of the 3 hypothetical ionic crystal can be calculated.
Ca
(s)
+ ½Cl
2(g)
→ Ca
+
Cl
-
(s)
∆H
f
o = -155 kJmol
-1

Ca
(s)
+ Cl
2(g)
→ Ca
2+
(Cl
-
)
2(s)
∆H
f
o = -763 kJmol
-1

Ca
(s)
+
3
2
Cl
2(g)
→ Ca
3+
(Cl
-
)
3(s)
∆H
f
o = +1356 kJmol
-1


The enthalpy of formation of CaCl
2(s)
is most exothermic among the three. This explain why calcium chloride has
the empirical formula CaCl
2
because CaCl
2(s)
is the most stable one among the three.

The octet rule only helps to predict the formation of Ca
2+
ion but it doesn't offer explanation. The rationale behind
the formation of Ca
2+
ion is solely from an energetic point of view.

Glossary
lattice energy electron affinity Born-Haber cycle intermediate type of bond

III. Energetics of formation of ionic compounds Page 4

Past Paper
Question
92 1A 3 d
94 1A 1 a i ii iii
96 2B 5 a i ii
98 1A 1 c i
99 2A 1 a ii

92 1A 3 d
3d Briefly describe and explain the change in the lattice energy of Group I chlorides on descending the group. 3
The lattice energy decreases in magnitude on descending the group. NaCl 771; CsCl 645 kJ mol
-1
1 mark
This is due to increasing size of cation results in smaller attraction between cation and anion. 2 marks


94 1A 1 a i ii iii
1a i Write an equation to represent the change related to the second electron affinity of oxygen. 1
O
-
(g)
+ e
-
→ O
2-
(g)
1 mark
ii The first and second affinities of oxygen are -142 kJmol
-1
and +791 kJmol
-1
respectively. Explain why they have
opposite signs.
2

Addition of an e
-
to the O
(g)
is exothermic Q attraction between the nucleus and the incoming e
-
outweighs the
repulsion between the e
-
in O atom and the incoming e
-
. 1 mark
After addition of an e
-
, the size of O expands, hence the attraction for another electron is weakened, and the
repulsion between the O
-
(g)
ion and the e
-
makes the second electron affinity an endothermic process. 1 mark

iii Explain why all the inert gases have positive first electron affinities. 1
Screening effect of the stable p
6
configuration of inert gases (s
2
in the case of He) makes the addition of an extra e
-

an unfavourable process ∴ inert gases have +ve first E.A. 1 mark

C It was surprising to find that many candidates could not distinguish between electron affinity and electronegativity
and hence they performed badly in this part.


96 2B 5 a i ii
5a The first electron affinities of chlorine and bromine are -364 kJmol
-1
and -295 kJmol
-1
respectively.
i What is the meaning of 'electron affinity' ? 2
Electron affinity is the molar enthalpy change ½ mark
for the following process at standard state/conditions ½ mark
X
(g)
+ e
-
→ X
-
(g)

Or
electron affinity of an element X is the enthalpy change ½ mark
when 1 mole of X
-
(g)
is formed from gaseous atoms of X 1 mark
under standard conditions. ½ mark

C Most candidates did not give a precise definition for 'electron affinity'. They did not point out that the electron
affinity of an element X is the molar enthalpy change when atoms of X in the gaseous state take up electrons to
form X
-
(g)
ions under standard conditions.

ii Explain why the first electron affinity of chlorine is more negative than that of bromine. 2
Cl has a smaller size / a smaller no. of electron shells 1 mark
∴ Cl can exert a stronger attraction on an extra electron 1 mark


98 1A 1 c i
1c The theoretical lattice enthalpies of NaCl
(s)
and AgCl
(s)
, and the experimental lattice enthalpy of AgCl
(s)
are given
in the table below.

Compound Theoretical lattice enthalpy Experimental enthalpy
NaCl
(s)
- 770 ?
AgCl
(s)
- 833 - 905
i Calculate the experimental lattice enthalpy of NaCl
(s)
using the following thermochemical data.
∆Ho/kJ mol
-1

Atomization enthalpy of Na
(s)
108
First ionization enthalpy of Na
(g)
495
Bond dissociation enthalpy of Cl
2(g)
239
Electron affinity of Cl
(g)
- 349
Enthalpy change of formation of NaCl
(s)
- 411
3

III. Energetics of formation of ionic compounds Page 5
99 2A 1 a ii
1a ii Using the thermochemical data given below, calculate the lattice enthalpy of rubidium chloride.
∆Ho
298
/ kJ mol
-1

Rb
(s)
→ Rb
(g)
82
Rb
(g)
→ Rb
+
(g)
+ e
-
403
Cl
2(g)
→ 2Cl
(g)
242
Cl
(g)
+ e
-
→ Cl
-
(g)
-348
2Rb
(s)
+ Cl
2(g)
→ 2RbCl
(s)
-861


IV. Gibbs free energy change (∆G) Page 1
Topic IV. Gibbs free energy change (∆G)

Reference
Reading
3.0
Modern Physical Chemistry ELBS pg.
Chemistry in Context, 5th Edition ELBS pg. 339–350
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg.

Assignment
Reading


Syllabus
Gibbs free energy change

Notes
IV. Gibbs free energy change (∆G) (not required in A-Level)

So far, we have applied the concept of energetic to different chemical systems such as ionization energy, bond
energy and lattice energy. However, in certain instances, changes in enthalpy are only part of the driving force for
the change. Some processes take place spontaneously even though they are endothermic. i.e. ∆H > 0.

The observation seems to be contradictory, the products of an endothermic change is less stable than the reactants.



A. Limitation of enthalpy change (∆H)


For example, melting is an endothermic change. Ice
melts readily at room temperature. Although the heat
content of water is higher than ice, does that mean ice is
more stable than water ? If ice is more stable than water,
why does it change to water ?

Therefore, enthalpy change ∆H, is not a very good
description of the relatively stability of systems.
∆H
Ice
Water
melting
process


B. Entropy (S) and entropy change (∆S)


Consider another example, the free expansion of a balloon in
vacuum.

Since no work is done in the expansion, the temperature will
remain constant, i.e. ∆H = 0. The size of the balloon increases
and more spaces are available for the gaseous molecules to
travel. Therefore, the arrangement and the movement of the
molecules are getting more random.
free ansion in vacuum exp
 → 


The expansion is spontaneous which means that the bigger balloon is more stable than the smaller balloon though
the ∆H is 0. It can be generalized that the state with a high degree of disorderness is always favourable in nature.
The scientist called the disorderness in arrangement of a system – entropy S and the change in the disorderness –
entropy change ∆S.

In the above example, the arrangement of the molecules becomes more random and the entropy of the system
increases. i.e. ∆S > 0.

IV. Gibbs free energy change (∆G) Page 2


C. Gibbs free energy change (∆G)


In order to address the limitation of enthalpy change ∆H in describing the relative stability of different systems.
The scientist J. Willard Gibbs defined another function – Gibbs free energy change ∆G.

Gibbs free energy change is defined as

∆G = ∆H - T∆S where ∆H is enthalpy change
T is temperature in Kelvin
∆S is entropy change

For example, ice has a more ordered packing that water. Thus, melting is a process associated with an increase in
disorderness i.e. ∆S > 0.

Enthalpy change (∆H) of melting = 6010 kJmol
-1

Entropy change (∆S) of melting = 22.0 kJmol
-1



Temperature ∆H of melting -T∆S of melting ∆G of melting

-10ºC (263.15K) 6010 kJmol
-1
-5790 kJmol
-1
220 kJmol
-1


0ºC (273.15K) 6010 kJmol
-1
-6010 kJmol
-1
0 kJmol
-1


10ºC (283.15K) 6010 kJmol
-1
-6230 kJmol
-1
-220 kJmol
-1



Obviously, whether ice will melt or freeze is depending on temperature. At any temperature above 0ºC, ice tends to
melt. At any temperature below 0ºC, water tends to freeze. Moreover, the value of ∆G is always smaller than zero.

All spontaneous changes take place in the direction of decrease in free energy. i.e. ∆G < 0.

However, free energy change ∆G only indicates the energetic stability of a system. Whether the change will take
place is also depending on the kinetic stability of the system which will be discussed in the chapter of rate of
reaction.

Glossary
spontaneous reacton disorderness entropy (S) entropy change (∆S)
Gibbs free energy change (∆G)

Past Paper
Question


Chemical Bonding Page 1
Chemical Bonding

I. Shape of molecule
A. Lewis structure of molecule
1. Oxidation no. of individual atoms in a molecule
2. Formal charge of individual atoms in a molecule
3. Limitation of octet rule
B. Valence Shell Electron Pair Repulsion Theory (VSEPRT)
1. Octet expansion of elements in Period 3
2. Position of lone pair
3. 3-dimensional representation of molecular shape
C. Hybridization Theory
1. Overlapping of atomic orbital
2. Hybridization theory
3. Examples
a) sp hybridizaion
b) sp
2
hybridizaion
c) sp
3
hybridizaion
d) sp
3
d hybridizaion
e) sp
3
d
2
hybridizaion
4. Structure and shape of hydrocarbons
a) Characteristic of Carbon-Carbon bond
b) Shape of hydrocarbons
(1) Saturated hydrocarbons
(2) Unsaturated hydrocarbons
(3) Aromatic hydrocarbons
(a) Delocalization of π-electrons
(b) Stability of benzene
D. Molecular Orbital Theory
II. Ionic bonding
A. Strength of ionic bond - lattice energy
B. X-ray diffraction
1. Electron density map of sodium chloride
C. Periodicity of ionic radius
1. Definition of radius
2. Periodicity of ionic radius
3. Size of isoelectronic particles
Chemical Bonding Page 2
III. Covalent bonding
A. H
2
+
ion
B. Electron diffraction
C. Covalent radius
1. Definition of covalent radius
2. Addivity of covalent radius
3. Breaking down of addivity in covalent radius and bond energy
a) Resonance
(1) Resonance structure of benzene
(2) Resonance structure of nitrate ion
(3) Rules in writing resonance structures
b) Breaking down of addivity in bond enthalpies
(1) Delocalization energy
D. Dative covalent bond
1. Examples of H
3
N→BF
3
and Al
2
Cl
6

a) H
3
N→BF
3

b) Al
2
Cl
6

IV. Bonding intermediate between ionic and covalent
A. Differences between ionic bond and covalent bond
B. Incomplete electron transfer in ionic compound
1. Electron density map of LiF comparing with those of NaCl and H
2

2. Difference among lattice energies of Na, Ag and Zn compounds
a) Lattice energies of sodium halide, silver halide and zinc sulphate
b) Bonding intermediate between covalent and ionic
3. Polarization of ionic bond
a) Fajans’ Rules in polarization of ionic bond
C. Electronegativity
1. Definition of electronegativity
2. Pauling scale of electronegativity
D. Polarity in covalent bond
1. Deflection of a liquid jet by an electric field
2. Dipole moment
a) Vector quantity of dipole moment
b) Polarity of molecule
c) Factors affecting dipole moment
(1) Inductive effect (I)
(2) Mesomeric effect / resonance effect (R)
(3) Presence of lone pair

V. Metallic bonding
A. Electron sea model of metal
B. Strength of metallic bond
C. Melting and boiling of metal
D. Strength of ionic bond, covalent bond and metallic bond
I. Shape of molecule Unit 1 Page 1
Topic I. Shape of molecule Unit 1

Reference
Reading
4.0–4.1
Modern Physical Chemistry ELBS pg. 84–86
Organic Chemistry, Solomons, 6th Edition pg. 8–14

Syllabus
Lewis structure

Notes
Chemical Bonding

I. Shape of molecule

The shape of a molecule can be predicted and explained by several different theory

i. Valence Shell Electron Pair Repulsion Theory – repulsions among electron centres (bond pair and lone pair
electrons) have to be minimized.
ii. Hybridization Theory – overlapping of hybridized atomic orbitals
iii. Molecular Orbital Theory – overlapping of atomic orbitals to form molecular orbital


A. Lewis structure of molecule

Before the shape of a molecule can be derived, it would be easier to draw the Lewis structure (cross-dot diagram)
of the molecule first.

Steps of drawing Lewis structure

i. Determination of central atom
Not all atoms can be the central atom in a molecule. e.g. in H
2
O, H can only be the peripheral atom since it
can form only 1 bond.

ii. Determination the no. of the bonds have to be formed.

Count the electron available
Count the number of valence electrons provided by each atom. If the molecule is negatively charged, add extra
no. of electrons accordingly. If the molecule is positively charged, subtract the no. of electrons accordingly.

Count the electron required
Count the total no. of electrons required if the outermost shells of all the atoms have to be filled. e.g. in NH
3
,
there should be 8 electrons for N and 2 electrons for each H atom.

Determine the no. of bonds
The total no. of bond pairs can be calculated by the following method.
Assuming each atom in the molecule needs the max. no. of e
-
to fill its valence shell e.g. 2 for H, 8 for O or N.
Formation of each bond can save the use of 2 electrons.
no. of bond pair = (no. of electron required - no. of electron available) ÷ 2
e.g. NH
3
no. of bond pair = ((2 × 3 + 8) - 8) ÷ 2 = 3
e.g. NO
3
-
no. of bond pair = ((8 × 4) - 24) ÷ 2 = 4

iii. Drawing the skeleton of the molecule
Within a covalent molecule, there should be at least 1 bond pair between 2 atoms.

iv. Put the rest of the electrons into the diagram until octet is fulfilled and include the charge if any.

I. Shape of molecule Unit 1 Page 2


Examples


NH
3
i.
Central
atom – N

ii. N 5
3H 1 × 3
e
-
available 8

N 8
3H 2 × 3
e
-
required 14

no. of bond = (14 - 8) ÷ 2 = 3

iii.
N
H
H H

Total 8
3 N–H 6
Remaining 2
iv.
N
H
H H

3 N–H 6
1 lone pair 2
Total 8


NH
4
+
i.
Central
atom – N
ii. N 5
4H 1 × 4
+1 (charge) -1
e- available 8

N 8
4H 2 × 4
e
-
required 16

no. of bond = (16 - 8) ÷ 2 = 4

iii.
N
H
H H
H

Total 8
4 N–H 8
Remaining 0

iv.
N
H
H H
H
+

4 N–H 8
Total 8

NO
3
-
i.
Central
atom – N
ii. N 5
3O 6 × 3
-1 1
e- available 24

N 8
3O 8 × 3
e- required 32

no. of bond = (32-24)÷2 = 4

iii.
N O O
O

Total 24
3 N–O 6
Remaining 18
iv.
-
N O O
O

1 N=O 4
2 N–O 4
8 lone pairs 16
Total 24


1. Oxidation no. of individual atoms in a molecule

Oxidation no. – The difference between the number of electrons associated with an atom in a compound as
compared with an atom of the element.

Oxidation no. is related to the difference in electronegativity of the atoms in the molecule. It is assumed that the
bonding electrons will be attracted to the more electronegative atom from the less electronegative. i.e. the more
electronegative atom will has more electrons than if neutral, results in negative oxidation no.


e.g. CO
2


C O O

Oxygen is more electronegative than carbon, the 4 electrons in the double bond is attracted
towards the oxygen.

Oxidation no. of oxygen = no. of electron in neutral O atom - no. of electrons on O in CO
2

= 6 - 8 = -2
Oxidation no. of carbon = no. of electron in neutral C atom - no. of electrons on C in CO
2

= 4 - 0 = +4


e.g. NO
3
-

-
N O O
O

Oxygen is more electronegative than nitrogen

O.N. of the doubly bonded oxygen = no. of e
-
in neutral O atom - no. of e
-
on O in NO
3
-

= 6 - 8 = -2
O.N. of the singly bonded oxygen = no. of e
-
in neutral O atom - no. of e
-
on O in NO
3
-

= 6 - 8 = -2
O.N. of nitrogen = no. of e
-
in neutral N atom - no. of e
-
of N in NO
3
-

= 5 - 0 = +5


2. Formal charge of individual atoms in a molecule

I. Shape of molecule Unit 1 Page 3
Unlike oxidation no., formal charge is independent of difference in electronegativity. Formal charge of an
atom is calculated by assuming that the bond pair electrons are shared equally between the two atoms bonded
together.


e.g. CO
2


C O O

Formal charge of oxygen = no. of e- in neutral O atom - no. of e- associated with O in CO
2

= 6 - 6 = 0
Formal charge of carbon = no. of e- in neutral C atom - no. of e- associated with C in CO
2

= 4 - 4 = 0


e.g. NO
3
-

N O O
O
-
-
+

Formal charge of the doubly bonded oxygen
= no. of e
-
in neutral O atom - no. of e
-
associated with O in NO
3
-

= 6 - 6 = 0
Formal charge of the singly bonded oxygen
= no. of e
-
in neutral O atom - no. of e
-
associated with O in NO
3
-

= 6 - 7 = -1
Formal charge of nitrogen = no. of e
-
in neutral N atom - no. of e
-
associated with N in NO
3
-

= 5 - 4 = +1


Non-zero formal charge is usually indicated on the Lewis structure.
Similar to oxidation no., the sum of formal charges equals the overall charge carried by the
molecule.


To minimize the fuzziness of calculation, some formal charges of some atoms can be memorized.



N.B. The positive sign and negative sign must be accompanied for all oxidation no. and formal charges.

I. Shape of molecule Unit 1 Page 4


3. Limitation of octet rule

The forth-mentioned method of drawing Lewis structure is only limited to the elements in Period 2. This is
because, for principal quantum number 2, there are only 2s, 2p
x
, 2p
y
and 2
z
orbitals available. Each orbital can
accommodate 2 electrons and makes up to a total of 8.

Though the largest no. of valence electron would be 8, the no. can be less than 8.

For example, in NO
2
,
N O O
-
+
there are totally ( 5 + 6 + 6 ) = 15 valence electrons which is an odd number. It is
not possible for all atoms to have an octet structure. Actually, there are 8 electrons about each O atom and only 7
eletrons about N.


However, for period 3 elements, there are 3d orbitals available which is capable to accommodate 10 more
electrons. This is why P can form both PCl
3
and PCl
5
but N can only form NCl
3
. This phenomenon is called
expansion of octet (or expansion of coordination sphere) and will be explained in the chapter of hybridization
theory.

For those which does not obey octet rule, e.g. PCl
5
, SO
2
, another method have to be used to draw the Lewis
structure.

It is assumed that all valence electrons are capable to form bond with peripheral atoms. And the peripheral will
form the required number of bond to achieve octet.

e.g. in PCl
5
, P has 5 valence electrons and each Cl is capable to form 1 single bond. Therefore, the Lewis structure
will become
P
Cl
Cl Cl
Cl
Cl
.

e.g. in SO
2
, S has 6 valence electrons and each O is capable to form 1 double bond. Therefore, the Lewis structure
will become
S O O
.

e.g. in SO
4
2-
ion, S has 6 valence electrons ; 2 O atoms with 0 formal charge each forming 2 bond ; 2 O atoms with
-1 formal charge each forming 1 bond. Therefore, the Lewis structure will become
S
O O
O
-
O
-
.

e.g. XeF
4
is a noble gas compound not obeying octet rule. Xe has 8 outermost electrons, each F is capable to form
1 bond. As a result, 4 electrons about Xe will remains as the lone pairs. Therefore, the Lewis structure will
become
Xe
F
F
F
F
.


However, for some structures do not obey octet rule, sometimes memorization is required.

Glossary
Lewis structure Oxidation no. formal charge

Past Paper
Question
92 2B 6 Aa i 92 2B 6 Ba i

92 2B 6 Aa i
6Aa
i Write the formula in each case of ONE compound or ion in which nitrogen has the oxidation state +5, +3, -1 and
-3.
2
NO
3
-
, NO
2
-
, NH
2
OH, NH
3
½ mark each

92 2B 6 Ba i
6Ba
i Write the formula in each case of ONE compound or ion in which sulphur has the oxidation state -2, +2, +4 and
+6.
2
S
2-
, S
2
O
3
2-
, SO
3
2-
, SO
4
2-
½ mark each

I. Shape of molecule Unit 2 Page 1
Topic I. Shape of molecule Unit 2

Reference
Reading
Modern Physical Chemistry ELBS pg. 84–86
Physical Chemistry, Fillans pg. 126–143
Organic Chemistry, Solomons, 6th Edition pg. 9–14
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 125–128, 131–132
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 90–92

Syllabus
4.2
Shape of molecule
Valence Shell Electron Pair Repulsion Theory


Notes
B. Valence Shell Electron Pair Repulsion Theory (VSEPRT)

The shape of a molecule was related to the number of electrons in the outer shell of the central atom.

1. Electron-pairs, whether in bonding orbitals or lone-pair orbitals, arrange themselves in space so as to minimize
their mutual repulsions.
2. The repulsion between lone-pair/lone-pair is greater than that between lone-pair/bond-pair which is, greater
than that between bond-pair/bond-pair.
3. Where there are more than four pairs of electrons to consider. the interactions where the electron-pairs make
an angle greater than 90° at the central atom are ignored.

No. of electron
centre in the outer
shell of the central
atom

Shape of the
framework

Bond angle

Example
2 linear

180º BeCl
2


3

trigonal planar



120º


BF
3



4


tetrahedral



109º28'

CH
4

NH
3

H
2
O




5



trigonal bipyramidal




120º
90º


PF
5

SF
4

ClF
3



6


octahedral



90º


SF
6

IF
5




7



pentagonal
bipyramidal



72º
90º



IF
7


Note: An electron centre can either be a lone pair, single bond, double bond or triple bond.

I. Shape of molecule Unit 2 Page 2


1. Octet expansion of elements in Period 3

Elements in period 3 and onwards are capable to use the low lying energy d-orbitals available to form more bonds.
Therefore, the element in period 3 can exceed the octet by expansion of its coordination sphere. This would be
further explained in hybridization theory.

2. Position of lone pair


For the molecule with 5 electron centres, the lone pair
always occupies the equatorial position to minimize the
repulsion.

Since lone pair electrons, comparing with bonding pair,
is closer to the central atom and has greatest repulsion
with other electron centres, only repulsions with the
lone pair need to be considered.

e.g. in SF
4
If the lone pair occupies the equatorial position, there
would be only 2 90º lone pair / bond pair repulsions.
If the lone pair occupies the axial position, there would
be 3 90º lone pair / bond pair repulsions.

The 120º repulsion is neglected as it is much weaker
than 90º repulsion.


Steps of using VSEPR theory to determine the shape of a molecule.

1. Draw the Lewis structure.
2. Count the number of electron centre around the central atom and choose the corresponding framework.
3. Put the electron centres (with the atom if applicable) on the vertex of the framework so that the repulsion
among them are minimized.
4. Determine the bond angle.

In the determination of the shape of a molecule, only the geometry of the atoms are considered. The position of the
lone pair is not counted.


3. 3-dimensional representation of molecular shape


a lone pair
a bond on the paper
a bond going into the paper
a bond coming out of the paper


Usually two bonds are used to defined the plane of the
paper and then the other bonds are added with respect to
this plane.


I. Shape of molecule Unit 2 Page 3


Example Lewis
structure
no. of electron
centre
Framework
chosen
Shape of molecule Bond angle

BF
3

B
F
F F

3 single bonds

Total : 3


trigonal planar
B
F
F F

∠ F–B–F : 120 º

CH
4

C
H
H
H
H

4 single bonds

Total : 4


tetrahedral
C
H
H
H
H

∠ H–C–H : 109½º

NH
3

N
H
H H

3 single bonds
1 lone pair

Total : 4


trigonal pyramidal
N
H
H
H

∠ H–N–H : ≈ 107º

H
2
O
O H H

2 single bonds
2 lone pair

Total : 4


angular / bent / V-shaped
O
H
H

∠ H–O–H : ≈ 105º


Although all CH
4
, NH
3
and H
2
O has 4 electron centres, they possess slightly different bond angle, 109½º, 107º and
105º respectively. 109½º is the angle for a perfect tetrahedral. However, the repulsion with lone pair is greater than
the repulsion with bond pair. The presence of a lone pair on N squeezes the bond angle to 107º, the two lone pairs
on O squeezes the bond angle even further to 105º


Example Lewis
structure
no. of electron
centre
Framework
chosen
Shape of molecule Bond angle

PCl
5


P
Cl
Cl Cl
Cl
Cl

5 single bonds

Total : 5


trigonal bipyramidal
P
Cl
Cl
Cl
Cl
Cl

∠ Cl–P–Cl : 120º × 3
∠ Cl–P–Cl : 90º × 6

SF
6

S
F F
F F
F F

6 single bonds

Total : 6

octahedral
S
F
F
F F
F F

∠ F–S–F : 90º

NH
4
+

N
H
H
H
H
+

4 single bonds

Total : 4


tetrahedral
N
H
H
H
H
+

∠ H–N–H : 109½º

NH
2
-

N H H
-

2 single bonds
2 lone pairs

Total : 4


angular / bent / V-shaped
N
H
H
-

∠ H–N–H : ≈ 105º

CO
2

O C O

2 double
bonds

Total : 2


linear
C O O

∠ O=C=O : 180º

SO
2

S O O

2 double
bonds
1 lone pair

Total : 3

angular / bent / V-shaped
S
O O

∠ O=S=O : ≈ 120º
I. Shape of molecule Unit 2 Page 4

Glossary
Lewis structure Oxidation no. formal charge Valence shell electron pair repulsion theory
octet expansion

Past Paper
Question
91 1A 3 d i ii 91 2B 5 e
92 1A 3 g i ii
93 1A 1 b i ii 93 1A 3 a ii
94 1A 1 c i ii
95 1A 2 e i ii
96 1A 2 b i ii
97 1A 3 b i ii iii
98 1A 3 a i ii iii 98 1A 4 a i 98 2A 1 c i
99 2A 3 c i

91 1A 3 d i ii
3d Draw the molecular shapes of
i PCl
5(g)
1

P
Cl
Cl
Cl
Cl
Cl
1 mark

ii SF
4(g)
1

S
F
F
F
F
1 mark


91 2B 5 e
5e Why is the bond angle in NF
3
smaller than that in NH
3
? 2
(Valence Shell Electron Pair Repulsion approach)
Bond pair electrons nearer to F than H ½ mark
since F is more electronegative ½ mark
∴ bond-pair/bond pair repulsion is smaller in NF
3
than in NH
3
. 1 mark
N
H
H H
N
F
F F

or
(Hybridization approach)
The primary scheme of hybridization of N is sp
3

the p orbital is more directional than s orbital and have been attracted strongly towards the electronegative F
as a result the N in NF
3
has higher s-character than N in NH
3

Bond angle ∝ s-character e.g. Ideal bond energy of following hybridization: sp = 180º, sp
2
= 120º, sp
3
= 109½º


92 1A 3 g i ii
3g Draw diagrams showing the shapes of the following molecules. Indicate the lone pairs (if any) on each central
atom.

i ICl
2


I
Cl
Cl
1 e
-
only

Linear shape 1 mark
Lone pairs ½ mark

ii XeOF
4


Xe
O
F
F
F
F
note: Xe is [Kr]4d
10
5s
2
5p
6

Square-pyramidal 1 mark
Lone pair ½ mark

I. Shape of molecule Unit 2 Page 5

93 1A 1 b i ii
1b For each of the following molecules, draw a three-dimensional structure and state the molecular geometry.
i SiF
4
2

Si
F
F
F
F
tetrahedral 2 marks

ii OF
2
2

O
F F
bent / V-shaped 2 marks


93 1A 3 a ii
3a Consider the following compound, X:


ii Suggest expected values for the bond angles α, β and γ. 1½
α: 108º-110º β: 178º-182º γ: 118º-122º ½ mark each

94 1A 1 c i ii
1c For each of the following molecules, draw a three-dimensional structure showing the positions of the bond
electron pairs and lone electron pairs (if any). In each case, state the molecular geometry and whether the
molecule possesses a non-zero dipole moment.

i BF
3
2

B
F
F F
1 mark
trigonal / triangular planar ½ mark
no dipole moment ½ mark

ii ClF
3
2

Cl
F
F
F
1 mark
T-shaped ½ mark
Possesses a net dipole ½ mark
[0 mark if shape of ClF
3
is described as triangular planar]


95 1A 2 e i ii
2e For each of the following species, draw a three-dimensional structure showing the bond electron pairs and lone
electron pairs of the central atom. State the shape of the species in each case.

i ICl
4
-


I
Cl
Cl
Cl
Cl
-
(1 mark, no charge -½ mark, no lone pair -½ mark)
Square planar ½ mark

ii SCl
2


S
Cl Cl
1 mark
V-shaped / bent / angular ½ mark


96 1A 2 b i ii
I. Shape of molecule Unit 2 Page 6
2b For each of the following chemical species, draw a three-dimensional structure showing the bond electron pairs
and lone electron pair(s) of the central atom underlined. State the shape of the species in each case.

i ClO
3
-


-
Cl
O
O
O

pyramidal 1½ mark
(Deduct ½ mark for omitting the negative charge)

ii NOF 1½

O
N
F

angular or V-shaped 1½ mark
(Deduct ½ mark for missing out the lone pair)
(1 mark for 3-D structure; ½ mark for the shape)


97 1A 3 b i ii iii
3b For each of the following sulphur-containing chemical species, state its shape and the oxidation state of sulphur. 3
i H
2
S
ii SO
2

iii SO
4
2-


98 1A 3 a i ii iii
3a For each of the nitrogen-containing chemical species below, state its shape and the oxidation state of nitrogen.
i NO
2
+
1
ii NH
3
1
iii NO
3
-
1

98 1A 4 a i
4a Alcohol E has the structure CH
3
CH(OH)C
2
H
5
.
i Draw a three-dimensional representation of E. 1

98 2A 1 c i
1c i Draw the three-dimensional structure of BF
3
. 4

99 2A 3 c i
3c Consider the hydrides of three Period 3 elements : SiH
4
, PH
3
and H
2
S
i For each hydride, draw a three-dimensional structure showing the bond electron pairs and lone electron pair(s), if
any, of the central atom.


I. Shape of molecule Unit 3 Page 1
Topic I. Shape of molecule Unit 3

Reference
Reading
Modern Physical Chemistry ELBS pg. 84–86
Physical Chemistry, Fillans pg. 126–143
Organic Chemistry, Solomons, 6th Edition pg. 26–37
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 133–140
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 419

Syllabus
4.3
Hydridization Theory

Notes
C. Hybridization Theory


Actually, the electrons in the molecule are not
stationary, they undergo wave like motion. The valence
shell electron pair repulsion theory is not good enough
to explain this. Therefore, the scientist developed
another theory, hybridization theory.
Questions that cannot be answered by VSEPRT
1. electrons are not stationary
2. the strength of the 2 bonds in a double bond are not
the same.
3. No. of unpaired e
-
available for bond formation.
4. shape of some molecules
5. strength of some bonds



1. Overlapping of atomic orbital

Instead of fixed electron centre, covalent bond is now viewed as an overlapping of atomic orbitals.



In hydrogen, two hydrogen 1s atomic orbitals are overlapped to form a covalent bond. The two 1s orbitals
interfere with each other constructively. This causes a higher electron density along the internuclear axis and
create the attraction to bring the two atoms together.


There are two kinds of overlaps i. head-on overlap
ii. sideway overlap


Head-on overlap (End to End overlap) of the orbital
give σ (sigma) bond.




Sideway overlap (Laterally overlap) of the orbital give
π (pi) bond.




Since the bond strength of a covalent bond is directly proportional to the area of overlap, in most of the case,
the σ bond will be stronger than the π bond. Also, the π electrons, unlike σ electrons, are not concentrated along
the internuclear axis.

In large atoms, π bonds are not favorable because, being removed from the line between the centres of the
atoms, the π bond rapidly weakens as the size of the atom increases. e.g. C=C double exists but Si=Si double bond
doesn't exist.
I. Shape of molecule Unit 3 Page 2


σ bond and π bond can be distinguished by the shape of their cross section. σ bond has a cylindrical cross section
about the bond axis but π bond does not has a cylindrical cross section.



Orbital representation of one σ bond and two π
bonds

Cross section

`

2. Hybridization theory

Hybridization means mixing.
Hybridization theory addresses many questions that cannot be explained by Valence Shell Electron Pair Repulsion
Theory.

i. electrons are not stationery, they undergo wave like motion.
ii. The strength of C=C (612 kJmol
-1
) is not twice of the strength of C–C (347 kJmol
-1
) bond. i.e. the two bonds
in double bond are not equvalent.
iii. There are not enough unpaired electrons in a C atom in ground state (1s
2
2s
2
2p
2
) for the formation of 4 single
bonds.
iv. The four single bonds in CH
4
are equivalent and the shape is tetrahedral.

Consider CH
4
molecule, experimental findings tell us that the 4 C–H bonds are equivalent and the molecule is
tetrahedral


A C atom in ground state has only 2 unpaired electron
in 2 different 2p orbitals which can only form 2 single
bond.

1s 2s 2p
ground state C
2 2 110

If one electron is promoted from 2s orbital to 2p orbital,
you will get 4 unpaired electrons for bond formation.

However, if the 4 unpaired electrons overlap with 1s
electron of the 4 H atoms independently, the bond
formed will not have equivalent strength. This is
because the 4 unpaired electrons are not equivalent. One
is a 2s electron and 3 are 2p electrons.

Furthermore, the bond angle will not be 109½º any
more. The angle between different p orbitals are only
90º.


1s 2s 2p
excited state C
*

2 1 111

Therefore, scientist proposed that the 4 unpaired
electrons interfere with each other first (i.e. mixed with
each other) to form 4 equivalent orbitals before any
bond is formed.
Because the new orbitals are formed from one s
orbital and three p orbital. They are called sp
3

hybridized atomic orbitals or sp
3
hybrid orbitals.

1s sp
3

hybridized C
*

2 1111




It can be seen that the main purpose of developing hybridization theory, or any new theory, is to explain the
experiemental findings.
I. Shape of molecule Unit 3 Page 3


The process of combining the orbitals is called hybridization.

Note : Hybridized atomic orbitals = atomic orbitals


no. of hybridized atomic orbitals = no. of atomic orbitals used



4 s -o rb i ta l
hybridization
excited
state
hybridized
atomic orbital
overlapping
of orbitals
(bond formation)
ground state
(more stable product)
promotion
∆H


In some of the hybridization processes, electron is
promoted to the higher orbital first. e.g. from 2s to 2p
orbital in C. This requires energy. Since bond formed
will be stronger with hybridization, this will be paid off
by the energy released during bond formation.

Since hybridization is just a kind of interference, only
the orbitals with similar energy can be hybridized. i.e.
2s orbital cannot hybridize with 3s orbital

Hybridized orbital No. of electron pairs
(bond & lone pairs)
Geometrical arrangement Typical examples
sp 2 Linear BeCl
2
, C
2
H
2
, CO
2

sp
2
3 Trigonal planar BeF
3
, C
2
H
4

sp
3
4 Tetrahedral CH
4
, NH
3
, H
2
O
sp
3
d or dsp
3
(not required) 5 Trigonal bipyramidal PCl
5

sp
3
d
2
or d
2
sp
3

(not required)
6 Octahedral Fe(CN)
6
3+
,SF
6

* Table needed to be remembered.


3. Examples

a) sp hybridization

e.g. C
2
H
2
(linear)


At first, one 2s electron is promoted to 2p orbital.

One 2s orbital and one 2p orbital undergo hybridization
to form two hybridized orbitals.

sp hybridized orbitals consists of two lobes with linear
geometry.


1s 2s 2p

ground state C
2 2 110

1s 2s 2p
promotion
 → 
excited state C
*

2 1 111

1s sp 2p
hybridization
 → 
hybridized C
*

2 11 11

One sp hybridized orbital overlaps with the 1s orbital of
H to form a C–H σ bond.
Another sp hybridized orbital overlaps with the sp
hybridized orbital of another C to form a C–C σ bond.



The two p orbitals on one C overlap with the two p
orbitals of another C laterally to form 2 C–C π bond.

It can be seen that not all the three C–C bond are
equivalent.

Because of the cylindrical symmetry of the σ bond, the
C–H bond is free to rotate. Rotation of the C≡C bond
will break the two π bonds, therefore C≡C bond is not
free to rotate.

Orbital representation of ethyne (H–C≡C–H)
I. Shape of molecule Unit 3 Page 4


b) sp
2
hybridization

e.g. BF
3
(trigonal planar)

1s 2s 2p 1s 2s 2p
ground state B
2 2 100

promotion
 → 
excited state B*
2 1 110
1s sp
2
2p

hybridization
 → 
hybridized B*
2 111 0


The three sp
2
hybridized orbitals overlap with 2p
orbitals of the three fluorine to form 3 σ bonds.

sp
2
hybridized orbitals consists of three lobes with
trigonal planar geometry.

On B, there is still an empty 2p orbital and it does not
fulfill octet. BF
3
is an electron deficiency species and
ready to accept electron from other molecule.


one 2s and two 2p orbitals sp
2
hybridized orbitals


e.g. C
2
H
4
(trigonal planar)

1s 2s 2p 1s 2s 2p
ground state C
2 2 110
promotion
 → 
excited state C
*

2 1 111
1s sp
2
2p

hybridization
 → 
hybridized C
*

2 111 1


Unlike BF
3
, the unhybridized p orbital of the C at right
angle to the plane has an unpaired electron. The p
orbitals from the two C overlap laterally to form a π
bond.

Since the π bond is not free to rotate, ethene has a
planar structure.


I. Shape of molecule Unit 3 Page 5


c) sp
3
hybridization

e.g. CH
4
(tetrahedral)

1s 2s 2p 1s 2s 2p
ground state C
2 2 110
promotion
 → 
excited state C
*

2 1 111
1s sp
3


hybridization
 → 
hybridized C
*

2 1111


sp
3
hybridized orbitals consists of four lobes with
tetrahedral geometry directed to the four vertices of a
tetrahedron.

CH
4



e.g. NH
3
(trigonal pyramidal)

1s 2s 2p 1s sp
3

ground state N
2 2 111
hybridization
 → 
hybridized N
2 1112


One of the sp
3
hybridized orbital is occupied by an
electron pair. This is the lone pair electrons of the
molecule.
NH
4



e.g. H
2
O (angular)

1s 2s 2p 1s sp
3

ground state O
2 2 211
hybridization
 → 
hybridized O
2 1122



In CH
4
molecule, being symmetrical, adopts the bond angle of regular tetrahedron
109º29'.

In NH
3
molecule, the bond angle is decreased by 2.2º (106º45').
In H
2
O molecule, the bond angle is decreased by 5.0º (104º31') from the tetrahedral value.

The tend can be predicted by the valence shell electron pair repulsion theory which state
that the lone pair-lone pair repulsion is stronger than lone pair-bond pair repulsion and a
lone pair-bond pair repulsion is stronger than bond pair-bond pair repulsion.


H
2
O


It can be observed that the bond angle is related to the percentage of s character in the hybridized orbital.
sp – 180º (50% s character), sp
2
– 120º (33% s character), sp
3
– 109½º (25% s character)
The higher the s character, the larger will be the bond angle.

I. Shape of molecule Unit 3 Page 6


d) sp
3
d hybridization (not required in A-Level)

e.g. PF
5
(trigonal bipyramidal)
3s 3p 3d 3s 3p 3d
P [Ne]
2 111 00000
promotion
 → 
P
*
[Ne]
1 111 10000
sp
3
d 3d

hybridization
 → 
P
*
[Ne]
11111 0000


The hybridization process involves the promotion of an electron from 3s orbital to 3d
orbital.
The central atom, P, does not obey octet rule, this is known as expansion of the octet.

This is impossible for elements in period 2, as there is no low lying energy d orbital
available. i.e. Energy required to promote 2p electrons to 3s orbital will be large that
cannot be paid off in the bond formation process.



e) sp
3
d
2
hybridization (not required in A-Level)

e.g. SF
6
(octahedral) [Ne] 3s
2
3p
4

3s 3p 3d 3s 3p 3d
S [Ne]
2 211 00000
promotion
 → 
S
*
[Ne]
1 111 11000
sp
3
d
2
3d

hybridization
 → 
S
*
[Ne]
111111 000


The six sp
3
d
2
hybrid orbitals are identical. They overlap
with the p orbitals of the six fluorine atoms to form a
perfect octahedral.



e.g. XeF
4
(square planar) [Kr] 4d
10
5s
2
5p
6


5s 5p 5d 5s 5p 5d
Xe [Kr] 4d
10

2 222 00000
promotion
 → 
Xe [Kr] 4d
10

2 211 11000
sp
3
d
2
5d

hybridization
 → 
Xe [Kr] 4d
10

221111 000


Not all noble gases can form compound. As the principle quantum number
increases, the energy gap between the orbitals gets smaller. For heavy noble gas
atom, electron from lower energy level may be promoted to higher energy level to
yield unpaired electrons for bonding.
Xe
F
F F
F

I. Shape of molecule Unit 3 Page 7



Glossary
Lewis structure Oxidation no. formal charge Valence shell electron pair repulsion theory
octet expansion Hybridization theory σ(sigma) bond π(pi) bond ground state
excited state

I. Shape of molecule Unit 3 Page 8

Past Paper
Question
90 2B 4 d 90 2B 6 a i iii v
94 2B 4 c
95 1A 2 a
98 2B 5 a i

90 2B 4 d
4 Account for the following observations.
4d Oxygen usually forms compounds with oxidation numbers -2, -1 and 0, whereas sulphur can form compounds
with many more oxidation numbers ranging from -2 to +6.
3
Sulphur has empty low lying energy 3d orbital - to expand its coordination sphere, thus capable of forming
compounds with a wide range of oxidation number. 1 mark
Oxygen has a much higher electronegativity than S and therefore it usually acts as an oxidant. 1 mark
Oxygen cannot expand its octet/has no low lying energy orbital for bonding. 1 mark


90 2B 6 a i iii v
6a The following species are either impossible to prepare or very unstable. Explain, in each case, why this is so.
i NCl
4

Nitrogen cannot have 9e
-
in its valence shell and cannot expand its octet because N has no low lying energy
orbitals for bonding. 1½ mark

iii ArCl
2

Ar does not form compounds because of the stability of close-shell electronic configuration. 1½ mark
v [PO
4
]
2-

P cannot have oxidation state higher than +5. 1½ mark

94 2B 4 c
4c What is the highest oxidation state of iodine? Give an example of an iodine-containing compound in which iodine
is in this oxidation state.
2
Hightest O.S. of I = +7 1 mark
Example : IF
7
, IO
4
-
1 mark


95 1A 2 a
2a Explain why phosphorus can form PCl
3
and PCl
5
, while nitrogen can form only NCl
3
. 2
P has low-lying empty 3d orbital / energy level, promotion of e
-
to 3d, gives 5 unpaired electrons. It is capable to
form 5 covalent bond. 1½ mark
In N, there is no low-lying d orbitals, excitation of e
-
is not possible. ∴ It can form only 3 covalent bonds.
½ mark


98 2B 5 a i
5a Consider the following compound F.
CH CH CH
3
C CH
a b
c
d
F


5
i Give the hybridization states of the carbon atoms, a, b, c and d.

I. Shape of molecule Unit 4 Page 1
Topic I. Shape of molecule Unit 4

Reference
Reading
4.4
Principles of Organic Chemistry, Peter R.S. Murray, 2
nd
Edition pg. 14–23, 33–34, 122–129
Organic Chemistry, Solomons, 6
th
Edition pg. 52–59, 61–65
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 110–111, 141–143

Syllabus
The unique nature of carbon
Structure and Shape of hydrocarbons

Notes
4. Structure and shape of hydrocarbons

a) Characteristic of Carbon–Carbon bond

i. Bond strength

Comparing with other single bond, C–C bond is the one with the highest bond strength. Therefore, it is capable
to form a stable long chain molecule. This characteristic is called catenation of C atom.

Bond Bond energy
C–C +346 kJmol
-1

N–N +163 kJmol
-1

F–F +158 kJmol
-1

Cl–Cl +242 kJmol
-1

Br–Br +193 kJmol
-1

I–I +151 kJmol
-1


ii. Ability to form multiple bond

Furthermore, C is capable to form relative stable double bond and triple bond.
Bond Bond energy / kJmol
-1

C–C +346
C=C +610
C≡C +837

This make a lot of different kinds of connection possible in the organic molecule. There is over millions of
different organic compounds identified and may be billions not identified.



b) Shape of hydrocarbons

(1) Saturated hydrocarbons



In saturated hydrocarbons, all C atoms are tetrahedrally bonded. The arrangement can be viewed as the repulsion
of the four bonding electron pairs or the result of sp
3
hybridization.

Furthermore, since σ bond has cylindrical (circular) cross section and the area doesn't change when the bond
rotates, all σ bond are free to rotate.


Shape of methane

Shape of ethane
I. Shape of molecule Unit 4 Page 2


(2) Unsaturated hydrocarbons


Rigidity of double and triple bond – Rotation of the C=C and C≡C bonds will break the one π bond and two π
bonds respectively, therefore C=C and C≡C bond are not free to rotate.


Shape of ethene (H
2
C=CH
2
)

Shape of ethyne (H–C≡C–H)


(3) Aromatic hydrocarbons


By X-ray diffraction, it was found that the six C–C
bonds in benzene are equivalent and with the bond
length intermediate between single C–C bond and
double C=C bond.
Kekulé structure
Type of bond Bond length / nm
Single C–C 0.154
Benzene C–C 0.139
Double C=C 0.134
Triple C≡C 0.120


According to energetic studies, the actual benzene is more stable that the Kekulé structure. This is due to the
delocalization of the π electrons / resonance of π electrons



(a) Delocalization of π-electrons

2s 2p
C ground state [He]
2 110

2s 2p
promotion
 →  C excited state [He]
1 111

sp
2
p
hybridization
 →  C sp
2
hybrid atomic orbital [He]
111 1


The six carbon atoms undergo sp
2
hybridization.
One lobe of each C sp
2
hybrid orbital overlaps with lobe of another C to form C–C σ bond.
Another lobe overlap with 1s orbital of H to form C–H σ bond.
The p orbitals overlap above and below the plane laterally to form an extensive π orbital. This gives benzene a
planar structure which guarantees maximium p orbital overlapping.


I. Shape of molecule Unit 4 Page 3


(b) Stability of benzene

Chemical properties of benzene, hexane, cyclohexane and cyclohexene

H
H
H
H H
H





H H
H H
H
H
H
H H
H
H
H

H H
H H
H
H
H
H
H
H


Benzene Hexane Cyclohexane Cyclohexene


Reaction Benzene Hexane Cyclohexane Cyclohexene

bromine in CCl
4

(in dark)
No reaction.
Br
2
decolorizes
slowly only in the
presence of Fe
catalyst with
evolution of HBr.
(Electrophilic
substitution)
No reaction.
Upon heating,
Br
2
decolorizes
slowly with
evolution of
HBr.
(Radical
substitution)
Similar to
hexane.
(Radical
substitution)
Decolorize immediately.
(Electrophilic addition)

acidified potassium
manganate(VII)
KMnO
4(aq)
/H
+
(aq)

No reaction. No reaction. No reaction. Purple manganate(VII)
decolorize immediately.
(Oxidation)

neutral potassium
manganate(VII)
KMnO
4(aq)

No reaction. No reaction. No reaction. Purple manganate(VII) turns to
black ppt. of manganese(VI)
oxide, MnO
2(s)
.
(Oxidation)

alkaline potassium
manganate(VII)
KMnO
4(aq)
/OH
-
(aq)

No reaction. No reaction. No reaction. Purple manganate(VII) turns to
green manganate(VI), MnO
4
2-
(aq)
, immediately.
(Oxidation)


The chemical properties of benzene is so different from ordinary alkene e.g.(cyclohexene). It resembles the
properties of alkane instead. This is due to the extra stability from delocalization of π electrons.

For example, its reaction with bromine is a substitution reaction (electrophilic substitution) instead of addition
reaction (electrophilic addition) in other typical alkenes. This will be explained with more details in the section
of reaction mechanism.

Glossary
catenation electrophilic substitution electrophilic addition reaction mechanism

I. Shape of molecule Unit 4 Page 4

Past Paper
Question
93 1A 3 a i
94 2C 9 b i
96 1A 3 c i ii
97 1A 4 c I
99 2A 3 b

93 1A 3 a i
3a Consider the following compound, X:


i Give the hybridization state of the carbon atoms indicated by a, b and c. 1½
a: sp
3
b: sp c: sp
2
½ mark each

94 2C 9 b i
9b Ethene and chloroethene can undergo polymerization to give polyethene (PE) and polyvinyl chloride (PVC)
respectively. PVC is more rigid and durable than PE, but incineration of PVC causes a more serious pollution
problem.

i Describe the bonding and shape of the ethene molecule in terms of the type and spatial arrangement of the orbitals
involved.
3
There are 4 C–H bonds and 1 C=C bond in an ethene molecule.
The C’s in ethene are sp
2
hybdrized
The C–H bond is formed by overlapping of a sp
2
hybrid orbital with an atomic orbital of H. 1 mark
The C=C bond consisted of a s bond and a p bond. These bonds are formed by the overlapping of two sp
2
hybride
orbitals and of the two unhybridized p orbitals on C’s respectively. 1 mark
C C
H
H
H
H
π bond
σ bond

Since for sp2 hybridization, the hybrid orbitals are arranged on a triangular plane.
∴ Ethene molecule is planar and the C–C–H bond angles are 120º 1 mark


96 1A 3 c i ii
3c Consider the following structure :


i Give the hybridization states of the carbon atoms a, b and c. 1½
a: sp
3
, b sp, c: sp
2
3 × ½ mark
ii Suggest expected values for the bond angles α, β and γ. 1½
a : 108-110º, b : 180º, g : 119-121º 3 × ½ mark
(Deduct ½ mark for missing out the degree notation)


97 1A 4 c i
4c i Give the hybridization state of the carbon atoms and the bond angles in ethene. 3

99 2A 3 b
3b Briefly describe the bonding in benzene and give TWO pieces of supportive evidence.

I. Shape of molecule Unit 5 Page 1
Topic I. Shape of molecule Unit 5

Reference
Reading
Modern Physical Chemistry ELBS pg. 84–86
Organic Chemistry, Solomons, 6th Edition pg. 23–26

Syllabus
4.5
Molecular Orbital Theory

Notes
D. Molecular Orbital Theory (Not required in A-Level)

According to hybridization theory, all electrons in O
2
should be paired up.

1s 2s 2p 1s sp
2
2p
ground state O
2 2 211
hybridization
 → 
hybridized O
2 221 1

O undergoes sp
2
hybridization. The hybridized sp
2
orbital of the two O overlaps with each other to form a σ bond.
The unhybridized 2p orbitals of the overlaps laterally to form a π bond.

This approach fails to explain why liquid O
2
is paramagnetic, a phenomenon arisen from unpaired electron.

Scientist developed another theory called molecular orbital theory to explain this.


For example, in H
2
molecule, the two 1s orbitals can
interfere constructively to create a bonding molecular
orbital or destructively to create a anti-bonding
molecular orbital.

In bonding molecular orbital, the electron density is
concentrated along the internuclear axis, thus tends to
bring the two hydrogen atoms together.

In anti-bonding molecular orbital, the electron density is
concentrated on the two sides of the molecule, also
there is a node(an area with zero electron density)
between the two hydrogen atoms. This tends to break
the two hydrogen atoms apart.

As a result, bonding orbital has lower energy than anti-
bonding orbital.

Similar to Aufbau principle in building up of electrons,
the molecular orbital with lower energy will be filled
first.

Each molecular orbital can accommodate 2 electrons.
Electron pair in bonding orbital will have opposite spin
and electron pair in anti-bonding orbital will have
similar spin.






N.B. atomic orbital = molecular orbital


no. of atomic orbital = no. of molecular orbital

I. Shape of molecule Unit 5 Page 2


Molecular orbitals of oxygen

When the two oxygen atoms is approaching each other, the atomic orbitals start to overlap.
1s orbital is not involved in the overlapping since it is inner orbital.
The overlappings of 2s, 2p
x
, 2p
y
and 2p
z
give rise to 6 different energy levels.




The 12 electrons fill up the molecular orbitals according to the energy. 2 unpaired
electron can be found in the 2 degenerate anti-bonding π
*
2p molecular orbital.
This explain why oxygen is paramagnetic.

No. of electrons in bonding orbital = 10
No. of electrons in anti-bonding orbital = 6

Bond order = (no. of e
-
in bonding orbital - no. of e
-
in anti-bonding orbital) ÷ 2
= (10 - 6) ÷ 2
= 2


Glossary
Molecular orbital theory paramagnetism

Past Paper
Question


II. Ionic bonding Page 1
Topic II. Ionic bonding

Reference
Reading
4.7
Modern Physical Chemistry ELBS pg. 64–66
Chemistry in Context, 3rd Edition ELBS pg. 133, 192–195
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 99–104, 145–146, 149–151
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 83–86, 115–118, 125–127, 171–173

Syllabus
Strength of ionic bond
X-ray diffraction
Atomic and ionic size

Notes
II. Ionic bonding

Like all other kinds of bonding, ionic bond is a result of balance between attraction and repulsion.

There are electrostatic attractions among oppositely charged particle and repulsion among similarly charged
particle.

The ions will come to equilibrium when the attractive and repulsive forces balance one another an the ions will stay
in positions in the crystal lattice. The structure of ionic compound is called giant ionic structure or giant ionic
lattice.

II. Ionic bonding Page 2


Different ionic lattices







CsCl - Simple cubic NaCl - Face-centered cubic (Octahedral)

r
+
r
- = 0.933
r
+
r
- = 0.524


Two factors govern the packing of ions to form giant lattice:

i. Each ion tends to have the highest no. of neighbours of opposite charge, as this would increase the lattice
stability. The number of nearest neighbours is called the coordination umber of the central ion.
ii.. Relative sizes of the ions.

The arrangement of the ions in an ionic crystal is determined by the ionic radii ratio (r
+
/r
-
):

Coordination no. Shape r
+
/r
-
Example
8 Simple cubic 0.73 and above CsCl
6 Face centered cubic (Octahedral) 0.41 - 0.73 NaCl
4 Face-centered cubic (Tetrahedral) 0.22 - 0.41 ZnS


Ionic bonding is non-directional in nature. An ion is surrounded by many oppositely charged ions in all directions,
i.e. no particular orientation is favoured.

Characteristics of ionic compounds

1. Good electrolytes.
2. Hard solids because the inter-ionic forces within an ionic crystal are usually strong.
3. High melting point.
4. Soluble in water and insoluble in organic solvents.



A. Strength of ionic bond - lattice energy

By definition, mM
n+
(g)
+ nX
m-
(g)
→ M
m
X
n(s)
∆Ho
lat


Lattice energy can be served as a good estimate for the strength of the ionic bond. It has a typical value range from
600–1000 kJmol
-1
.

II. Ionic bonding Page 3


B. X-ray diffraction


The structure of an ionic crystal can be determined by a
technique called X-ray diffraction.

When X-rays strike a crystal, they are diffracted by the
electrons in the atoms or ions. The larger the atom, the
more electrons it possesses and the brighter the spot will
be on the diffraction pattern. From the pattern of spots
on the X-ray film, the distribution of electron in the
crystal can be calculated.

Points of equal density in the crystal are joined by
contours giving an electron density map.



1. Electron density map of sodium chloride

From the electron density map, it can be seen that
electrons are concentrated near the nuclei in ionic
compounds.

In NaCl, ions are not perfectly spherical but tend to
expand to fill up any empty space present, until their
charge clouds experience repulsion from that of the
neighbouring ions. The electron density between the
ions fall almost to zero.

Electron density map of sodium chloride



C. Periodicity of ionic radius

1. Definition of ionic radius

Ionic radius – the effective radius of ions in crystal lattices. It is the distance measured from the centre of the ion
to the region where the electron density is zero.

2. Periodicity of ionic radius

Similar to atomic radius, the size of an ion is mainly governed by the strength of the effective nuclear charge. On
top of this, it is also affected by the presence of other ions. If an ion is present in a surrounding with few ions
around, its electron cloud would tend to expand to fill up the space, until it is repelled by the electron clouds of
other ions

Size of cation
It is always smaller than the size of the corresponding atom as electron is removed. The proton to electron ratio
increases. The nuclear charge will have a greater effect on the fewer remaining electrons, which makes the
electron cloud contracts.

Size of anion
It is always bigger than the size of the corresponding atom as electron is added. The additional electron enters the
highest energy level without an increase in nuclear charge. This causes greater repulsion among the electrons.

The above discussion applies to simple ion only. Certainly, a polyatomic ion is much larger than a simple ion
because it contains a larger no. of atoms.

II. Ionic bonding Page 4


3. Size of isoelectronic particles

O
2-
ion, F
-
ion, Na
+
ion, Mg
2+
ion are said to be isoelectronic because they contain the same no. of electron and
have the same electronic configuration, – 2,8.

Therefore, their sizes show the order of O
2-
> F
-
> Na
+
> Mg
2+
.
Glossary
electrovalent bond coordination no. X-ray diffraction electron density map ionic radius
isoelectronic

Past Paper
Question
92 1A 3 b
95 2B 5 a ii iii
97 1A 1 c

92 1A 3 b
3b The size of three anions is in the order: Br
-
< H
-
< I
-
. Briefly explain why H
-
is smaller than I
-
, but larger than Br
-
. 2
I
-
has more e
-
shells ([Kr]5s
2
5p
6
) than H
-
(1s
2
). 1 mark
H
-
is large due to electron repulsion between 2 electrons in 1s orbital. 1 mark


95 2B 5 a ii iii
5a The table below lists some properties of the alkali metals.
Element Atomic
radius / nm
Ionic radius / nm First ionization
energy / kJmol
-1

Standard electrode
potential / V
Melting point / ºC
Li 0.123 0.060 520 -3.04 180
Na 0.157 0.095 495 -2.71 98
K 0.203 0.133 418 -2.92 64
Rb 0.216 0.148 403 -2.93 39
Cs 0.235 0.169 374 -2.95 29
ii Explain why the atomic radius is larger than the ionic radius in each element and why the ratio, atomic radius :
ionic radius is greatest in the case of Li.
3
The atom has one more electron shell than the cation. 1 mark
In M
+
, the nuclear charge outweighs the screening effect of the electrons and the electron cloud of M
+
experiences
a stronger attraction. Therefore, the ionic radii are smaller than the atomic radii. 1 marks
Atomic radius : ionic radius ratio is highest in the case of Li, because it has the smallest size. In Li
+
, the e
-

experience the strongest attraction ∴ contraction in size is greatest. 1 mark

iii Explain why the ionic radius of K
+
is larger than that of Ca
2+
, although they have the same electronic
configuration.
2
Electronic configuration of K
+
and Ca
2+
are both 1s
2
2s
2
2p
6
3s
2
3p
6
. 1 mark
Both number and arrangement of electrons are the same in two cations. Ca
2+
is doubly charged, while K
+
is singly
charged, the outermost e
-
in Ca
2+
experiences a stronger attraction (effective nuclear charge). Hence the radius of
Ca
2+
is smaller. 1 mark


97 1A 1 c
1c Arrange, with explanation, the following chemical species in the order of decreasing size.
F, O and O
-

3

III. Covalent bonding Page 1
Topic III. Covalent bonding

Reference
Reading
4.6.0–4.6.2
Modern Physical Chemistry ELBS pg. 78–82, 112–113
Chemistry in Context, 3rd Edition ELBS pg. 101–105
Organic Chemistry, Solomons, 5th Edition pg. 15–18, 506–509
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 114–115
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 86–90, 92–94

Syllabus
H
2
+
ion
Additivity of covalent radius
Breaking down of additivity due to resonance
Dative covalent bond

Notes
III. Covalent bonding

A. H
2
+
ion

For simplicity, H
2
+
ion can be used as the simplest model of covalent bond. In H
2
+
ion, only 1 electrons and 2
protons need to be considered.




There are only 3 forces involved.

1 repulsion term between the 2 protons and 2 attraction
terms between the electron and 2 protons.

The bond length (equilibrium distance between two
nuclei) depends on the balance of the repulsion and the
attraction.



Electron density map for the H
2
+
ion


The two positive nuclei are bond together by sharing the negative electron cloud. This arrangement leads to a
lower potential energy than if the electron cloud were not shared. And a lower P.E. results in greater stability.

Electron density is not uniform on the electron density map, but is greater along the internuclear axis. The high
concentration of electron between two positive nuclei serves to bind the nuclei together - covalent bond.


The attraction is even greater with the neutral H
2
molecule, where two electrons are available for bonding. This is
revealed in the decrease in the internuclear distance and increase in bond dissociation energy.

Internuclear distance (nm) Bond Dissociation energy (kJmol
-1
)
H
2
+
0.104 257
H
2
0.074 435
III. Covalent bonding Page 2


B. Electron diffraction

The electron density map of hydrogen cannot be obtained by X-ray diffraction / X-ray crystallography because
hydrogen is volatile and cannot be crystallized easily. And also, the electron density of the hydrogen atom is too
low to diffract the X-ray. Another similar method called electron diffraction is used to determine the structure of a
gaseous molecule.


When a beam of electrons is passed through a gas or
vapour at low pressure. The nuclei of atoms in gas
molecule scatter (diffract) the electrons.

From the diffraction pattern, the distance between
the nuclei and the structure of the molecule can be
determined.



C. Covalent radius

1 Definition of covalent radius

Covalent radius – half the distance between two atoms of the same kind held together by covalent bond.

2. Additivity of covalent radius

If there is a molecule A–B, the interatomic distance A–B is approximately equal to the arithmetic mean of the A–A
and B–B distance.
A B
A A B B
− =
− − +
2


and because of this simple relationship, it is possible to obtain interatomic distance of certain compound by simple
addition of covalent radii.

e.g. Average bond length of C–C bond : 0.154 nm
Bond length of H–H bond in H
2
: 0.074 nm
By calculation, bond length of C–H bond =
0.154 nm + 0.074 nm
2
= 0.114 nm
Average bond length of C–H bond determined by experiment : 0.108 nm
The two values rather agree with each other.



3. Breaking down of additivity in covalent radius and bond energy

This simple additive relationship of covalent radii was found to fail for certain molecules. e.g. benzene. The
reason is the molecules are actually resonance hybrid of two or more possible structures.
There are compounds whose bond length differ from calculated values. e.g. benzene and nitrate ion.

Compound Bond lengths (nm)
Calculated Experimental
benzene C=C 0.134 nm
C–C 0.154 nm
0.139 nm
NO
3


N–O 0.136 nm
N=O 0.115 nm
0.121 nm


All bond lengths are found to be equivalent. This is due to the delocalization of electrons / reasonance of electrons.
III. Covalent bonding Page 3


a) Resonance / Delocalization of electrons

(1) Resonance structure of benzene


In benzene molecule, six carbon atoms are joined together in a ring by
overlap of carbon sp
2
hybrid orbitals, forming C–C σ bonds. C–H σ bonds
are formed by further overlap with hydrogen 1s orbitals. the p-orbitals of
each carbon atoms overlap with each other to formal a new molecular
orbital. The electrons are delocalized in a system of π orbitals above and
below the ring. This make all the six C–C bonds equivalent.

Delocalization of electron is also called resonance of electrons. Two
Lewis structures are used to represent the real structure.

Resonance structures of benzene


Representation of hybrid
or



Since one π bond is shared between two C–C bonds, the bond order of the
C C
bond is said to be 1½ .



(2) Resonance structure of nitrate ion



Usually, formal charge is included in the resonance structure and the hybrid structure to see the distribution of the
electron.

Since one π bond is shared among three N–O bonds, the bond order of the
N O
bond is said to be 12 .


N.B. Resonance structures are only representations on paper. They do not exist. The real structure of the
molecule cannot be represented by any individual resonance structure. Furthermore, the electrons are not
shifting forth and back in the structure. Instead, they are evenly distributed in the structure.

Orbital representation is always the better way to represent the actual structure.

N O
O
O
sp
2
sp
2
sp
2
sp
2


(3) Rules in writing resonance structures

i. Resonance structures exist only on paper.
ii. In writing resonance structures, only electrons are allowed to move.
iii. The actual molecule or ion will be better represented by a hybrid of these structures.
iv. The energy of the actual molecule is lower than the energy that might be estimated for any contributing
structure.
III. Covalent bonding Page 4


b) Breaking down of additivity in bond enthalpies

The presence of delocalization of π electrons is further confirmed by the breaking down of addivitiy in bond
enthalpies.



C
C
C
C
C
C
H
H
H
H
H
H
or

H
H
H
H
H
H

or

Kekulé structure of benzene

German scientist Kekulé proposed that
benzene is a ring compound with alternating
C–C single bond and C=C double bond
joining the carbon atoms together.


To verify the validity of the structure, some reactions of benzene are studied. e.g hydrogenation

Hydrogenation of benzene
3H
2(g)
+
H H
H H
H
H
H
H H
H
H
H
H
H
H
H
H
H
(l)
Benzene Cyclohexane


Estimation of enthalpy of hydrogenation by bond energy terms


Bond broken Bond formed

3 C=C 3 C–C
3 H–H 6 C–H

E(C–H) +413 kJmol
-1

E(H–H) +436 kJmol
-1

E(C–C) +347 kJmol
-1
E(C=C) +612 kJmol
-1


∆H = energy required - energy released
= ΣE(bond broken) - ΣE(bond formed)
= (3 × E(C=C) + 3 × E(H–H)) - (3 × E(C–C) + 6 × E(C–H))
= (3 × 612 + 3 × 436) - (3 × 347 + 6 × 413)
= -375 kJmol
-1
(experimental value -210 kJmol
-1
)

The calculated value is so differed from the experimental value, less heat is released than the calculated value.
The difference between these values indicates that the actual structure of benzene is more stable than Kekulé
structure by (-210) - (-375) = 165 kJmol
-1


III. Covalent bonding Page 5


(1) Delocalization energy

This extra stability is attributed to the delocalization of the bonding electrons over all 6 carbon atoms.




The double bond electrons are not
localized at fixed positions, instead, they
delocalized around the ring and make the
6 C–C bonds equivalent. This
distribution minimizes the repulsion
among the electrons and give a more
stable structure.


H
H
H
H
H
H
or

Resonance structure of benzene
165 kJmol
-1
(delocalization energy)

-210 kJmol
-1
-375 kJmol
-1
H

The breakdown of the additivity rule demonstrates the importance of bond energy terms in understanding the
chemical bonding in benzene.
III. Covalent bonding Page 6


D. Dative covalent bond

Dative covalent bond – The linkage of two atoms by a pair of electrons, both electrons being provided by one of
the atoms.

The dative covalent bond is also known as coordinate bond. The formation of a dative bond requires an
unbonded(lone) pair of electrons in one atom (donor) and an empty orbital in another atom (acceptor).

1 Examples of H
3
N→BF
3
and Al
2
Cl
6


a) H
3
N→BF
3



Boron trifluoride does not possess an octet of electrons; this is a suitable
compound with which to introduce dative covalency.

BF
3
gas reacts with NH
3
gas to give a white solid with the composition
NH
3
BF
3
.



1s 2s 2p 1s 2s 2p
ground state B
2 2 100

promotion
 → 
excited state B*
2 1 110
1s sp
2
2p

hybridization
 → 
hybridized B*
2 111 0

B undergoes sp
2
hybridization and uses the three sp
2
hybridized orbitals to overlap with 2p orbitals of fluorine.
BF
3
has a planar structure and a vacant 2p orbital. The 2p orbital accepts the lone pair from NH
3
and the
hybridization of B changes from sp
2
to sp
3
.



b) Al
2
Cl
6


In gaseous state, two AlCl
3(g)
molecule dimerizes to form Al
2
Cl
6(g)
molecule.
3s 3p 3s 3p
Al [Ne]
2 100

promotion
 → 
Al
*
[Ne]
1 110
sp
2
3p

hybridization
 → 
hybridized Al
*
[Ne]
111 0



AlCl
3(g)
has a planar structure similar to BF
3(g)
. The vacant 3p orbital
accepts lone pair electrons on chlorine atom to form dative bond.

Al
Cl
Cl
Cl
Cl
Al
Cl
Cl



Glossary
Octet rule electron diffraction additivity of covalent radius resonance hybrid structure
delocalization delocalization energy dative covalent bond / coordinate bond

III. Covalent bonding Page 7

Past Paper
Question
92 2A 3 b iii 92 2B 5 a iii
95 1A 1 c
96 2A 1 a i ii
98 2A 1 c ii


92 2A 3 b iii
3b iii The covalent radius of carbon is 0.077 nm. The measured carbon-carbon bond length in benzene is 0.139 nm.
Estimate the carbon-carbon bond length in ethane. Explain any difference in the carbon-carbon bond lengths in
these two molecules.
3
C–C bond length of CH
3
–CH
3
= 2 × 0.077 = 0.154 nm 1 mark
C–C bond in ethane is a single bond which is longer than the carbon-carbon bond in benzene. In benzene, it is
because of delocalization electrons in the ring. The average bond order is larger than 1. 1 + 1 mark


92 2B 5 a iii
5a iii Draw resonance electronic structures of CO and CO
2
, showing lone pair electrons and charges where appropriate. 2

C O C O C O
Any 2 structures
C O O C O O C O O
Any 2 structures ½ mark each

C Very few candidates were able to draw resonance structures for CO and CO
2
. The charges on atoms in these
structures are neglected in many textbooks, but the students should be able to deduce these by "book-keeping" of
the lone pair and bond pair electrons.


95 1A 1 c
1c Account for the fact that the carbon-oxygen bond lengths in CO, CO
2
and CO
3
2-
are 0.113, 0.116 and 0.129 nm
respectively.
3

CO
C O
-
+
½ mark
Bond order = 3 / the bond formed between C & O is triple bond. It is the shortest. ½ mark
CO
2

C O O
½ mark
Bond order = 2 / the bond formed between C & O is double bond. ½ mark
CO
3
2-
It is a resonance hybrid of the following :
C
O
O O
-
-
C
O
O O
-
-
C
O
O O
- -
½ mark
Bond order = 1
1
3
(intermediate between C–C and C=C bond). It is the longest. ½ mark

C This question was not well answered. The answer required descriptions or diagrams of the electronic structures of
the three compounds and the deduction of the bond orders. It is more meaningful to show lone pairs of electrons,
and formal charges in these electronic structure diagrams. Many candidates could not give the correct structure for
CO, and few described the resonance of the CO
3
2-
structures.

III. Covalent bonding Page 8

96 2A 1 a i ii
1a For the hydrogenation of buta-1,3-diene,
H
2
C=CH–CH=CH
2(g)
+ 2H
2(g)
→ CH
3
CH
2
CH
2
CH
3(g)

the experimental molar enthalpy change is -239 kJmol
-1
.

i Estimate the molar enthalpy change for the above hydrogenation using the bond energy terms below :
Bond Bond energy term / kJmol
-1

H–H 436
C–H 413
C–C 346
C=C 611
2
∆H = -2E
C–C
- 4E
C–H
+ 2E
C–C
+ 2E
H–H
1 mark
or = -2(346) - 4(413) + 2(611) + 2(436) (1 mark)
= -250 kJmol
-1
1 mark
(0 marks for omitting the eve sign; deduct ½ mark for no units)

ii Explain why the estimated value differs from the experimental value. 2
Buta-1,3-diene is a conjugated system / delocalization of π electrons / resonance /
mesomerism occurs in buta-1,3-diene. 1 mark
or
C C
C C H
H H
H
H
H
(1 mark)
or

H
2
C CH CH CH
2
H
2
C CH CH CH
2
etc.
+
-
(1 mark)

The molecule is thus stabilized. ∴ energy released in hydrogenation is less than that in non-conjugated system.
1 mark

(Award 1 mark for the explanation: the bond energy given is only the average bond energy / bond energy of a
covalent bond depends on its bonding environment)

C Very few candidates related the difference in ∆H values to the delocalization of π electrons in the conjugated
system.


98 2A 1 c ii
1c ii BF
3
reacts with NH
3
to form an adduct, BF
3
·NH
3
. Account for the formation of the adduct and draw its three-
dimensional structure.


IV. Bonding intermediate between ionic anc covalent Page 1
Topic IV. Bonding intermediate between ionic and covalent

Reference
Reading
4.8
Chemistry in Context, 3rd Edition ELBS pg. 111–113
Organic Chemistry, Solomons, 6th Edition pg. 38–41
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 111–114
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 96–99, 162

Syllabus
Intermediate type of bond
Incomplete electron transfer in ionic compound
Electronegativity
Polarization of ionic bond
Polarity in covalent bond

Notes
IV. Bonding intermediate between ionic and covalent

A. Differences between ionic bond and covalent bond

The similarity in nature of ionic and covalent bonds is reflected by the same order of magnitude of lattice energies
(600-1000 kJmol
-1
) and covalent bond energies (300-1000 kJmol
-1
).

i. Distribution of electrons
In case of ionic solid, in certain region, the electron density between the ions fall almost to zero.
In case of covalent molecule, the electron density is highest between the bonding atoms and decreases
outwards. The electron density is concentrated along a line between 2 nuclei.

ii. Ionic compounds are formed by complete transfer of electron.
Covalent molecules are formed by sharing of electron among the bonding nuclei.

iii. In ionic compounds, oppositely charged ions attract electrostatically to one another. In covalent compounds,
the positive charged nuclei also attract electrostatically the electrons shared by the atoms involved. Moreover,
both of them are electrostatic in nature.



B. Incomplete electron transfer in ionic compound

1. Electron density map of LiF comparing with those of NaCl and H
2





NaCl (nearly purely ionic)





LiF
(intermediate between ionic and
covalent)






H
2
(purely covalent)


All the bonding arise from the interaction between the electrons and the nuclei. Different arrangements of the
electrons and atoms will give different kind of bonding.

From the electron density map, one can see that electrons are concentrated near the nuclei in ionic compounds
while there are substantial electron density between the nuclei of hydrogen atoms. In the LiF, its electron density
map shows that it is somewhere between a typical ionic compound and covalent compound.

IV. Bonding intermediate between ionic anc covalent Page 2


2. Difference among lattice energies of Na, Ag and Zn compounds

Besides the Born-Haber cycle, the lattice energies can also be calculated in terms of electrostatic interactions
among ions. The mathematical treatment of the calculation is beyond the scope of the syllabus, but it is worthy to
note the basic assumptions and the limitation of the model.

Further reading about the calculation of lattice energy can be found on pg. 71–73 of Modern Physical Chemistry
ELBS.

Assumptions of the mathematical model for calculation:

i. The geometrical arrangement of the ions within the crystal and the interionic distances are known. These can
be determined by a method called X-ray diffraction.
ii. The bonding within the crystal is completely ionic and all ions are spherical in shape, i.e. no sharing of
electron.



a) Lattice energies of sodium halide, silver halide and Zinc sulphide

Experimental lattice
Compound Theoretical lattice energy energy from Born-Haber cycle Percentage error
NaCl -777 kJmol
-1
-781 kJmol
-1
0.5 %
NaBr -731 kJmol
-1
-742 kJmol
-1
1.5 %
NaI -686 kJmol
-1
-699 kJmol
-1
1.9 %
AgCl -768 kJmol
-1
-890 kJmol
-1
15.9%
AgBr -759 kJmol
-1
-877 kJmol
-1
15.5%
AgI -736 kJmol
-1
-867 kJmol
-1
17.8%
ZnS -3427 kJmol
-1
-3615 kJmol
-1
5.5%

b) Bonding intermediate between covalent and ionic

In sodium halide, the theoretical values calculated from the mathematical model close to the values determined by
the Born-Haber cycle. This is because the difference in electronegativity between sodium and halogen is very
large, thus the electron transfer is almost complete and shows no evidence of electron sharing. This agrees with the
basic assumption of the model.

The great discrepancy of between the theoretical values and the experimental values of silver halides and zinc
sulphide implies that our model for calculation is not realistic.

Owing to the small size of the silver ion which polarizes the large halide ion easily, the bond possesses some
covalent characters. The experimental values also suggest that the bonds are stronger than the expected.

This is also an evidence of the presence of bonding intermediate between covalent and ionic.


IV. Bonding intermediate between ionic anc covalent Page 3


The discrepancies implies the presence of an appreciable proportion of covalent bonding.

Partial covalent properties is due to incomplete electron transfer in ionic compound and this is called polarization
of ions.

From spectroscopic studies of the vapours of alkali metal halides, the internuclear distance in these molecule is less
than in the corresponding ionic bond.

Halide Internuclear separation (nm)
Crystal Vapour
LiBr 0.275 0.217
LiI 0.300 0.239



This implies a stronger bond than in the crystal. This is
caused by a higher concentration of electron density
between the nuclei than in the crystal.

This arises from distortion of the electron cloud of one
ion or both from a spherical distribution.

Polarization of an ion representing a transition from
ionic bonding to covalent.




3. Polarization of ionic bond

When an ionic bond is formed between the cation X
+
and anion Y
-
, owing to its charge, the X
+
ion would tend to
attract the outer electrons in the charge cloud of Y
-
. This causes a displacement of the outer electrons of Y
-
back to
X
+
, so that the outer electron of X is not completely transferred to Y. The ionic bond formed is said to have some
covalent character.

a) Fajans’ Rules in polarization of ionic bond

i. The polarizing power of a cation is increased as (a) the size is reduced and (b) the charge is increased.
ii. The polarizability of anion increases as (a) the size increases and (b) the charge is increased.
iii. Covalent character is stronger for cations which do not have a noble gas electron arrangement (d electrons
have poor shielding properties). Thus Na
+
is less polarizing than Cu
+
. i.e. Ions of transition metal are usually
much smaller than the ions of main group metals)
IV. Bonding intermediate between ionic anc covalent Page 4


C. Electronegativity

1. Definition of electronegativity

Electronegativity – A measure of tendency of an atom in a stable molecule to attract electrons within a bond.

In H–Cl molecule, the bonding electrons are much closer to the chlorine than to the hydrogen; the chlorine being
the more electronegative atom.


2. Pauling scale of electronegativity

There are several method to measure the electronegativity of an element. One of the commonly used method is
Pauling scale of electronegativity.

Pauling defined the electronegativity of an atom as the power of that atom in a molecule to attract electrons. In
contrast with electron affinity, it is a measure of the power of an single gaseous atom to attract electrons.

In Pauling scale, 4 is assigned to the most electronegative atom, fluorine.

Pauling electronegativity values of some elements (The shaded ones are more electronegative than C)

H
2.1

Li
1.0
Be
1.5
B
2.0
C
2.5
N
3.0
O
3.5
F
4.0
Na
0.9
Mg
1.2
Al
1.5
Si
1.8
P
2.1
S
2.5
Cl
3.0
K
0.8
Ca
1.0
_ Ge
1.8
As
2.0
Se
2.4
Br
2.8
Rb
0.8
Sr
1.0
_ Sn
1.8
Sb
1.9
Te
2.1
I
2.5
Cs
0.7
Ba
0.9


In general, electronegativity values increase from left to right across each period and decrease down each group.


D. Polarity in covalent bond

1. Deflection of a liquid jet by an electric field


A dry glass rod rubbed with polythene develops a
positive charge. An ebonite rod rubbed with fur
develops a negative charge

A number of liquids are tested

Liquid showing Liquid showing
a marked deflection no or small deflection

Water
Trichloromethane Tetrachloromethane
Propanone
Ethoxyethane
Nitrobenzene Benzene
Cyclohexene Cyclohexane
Ethanol


IV. Bonding intermediate between ionic anc covalent Page 5


The zero or very small deflection with
tetrachloromethane is due to the symmetry of the
molecule in which the four dipoles counteract each
other exactly.

Molecules which do not possess a permanent dipole
moment are nevertheless polarised to some extent when
placed in an electrical field.



2. Dipole moment


If two charges of equal magnitude but opposite in sign,
+q and -q, are separated by a distance d, then the system
is said to have a dipole moment (µ) of magnitude give
by:
Dipole moment (µ)
= charge × distance between the +ve and -ve centres
= q × d

This dipole moment is usually expressed in terms of
Debye (D). 1 D ≈ 3.34 × 10
-30
Cm.

For example, in HCl, Cl attracts electrons more strongly
than H does, the dipole moment of the HCl is 1.1 D. Cl
is said to exert a negative inductive effect.




a) Vector quantity of dipole moment

Dipole moment is a vector quantity. For a molecule with more than one polar bond, the dipole moment of the
molecule is given by the vector sum of the dipole moments caused by the various polar bonds.

In asymmetric molecules (e.g. HCl, CH
3
CH
2
Cl), the center of the positive charge and the center of the negative
charge do no coincide and a permanent dipole moment results.


b) Polarity of molecule

The overall distortion of charge in molecules, which
results from unequal sharing of electrons, is known as
polarization. It represents the departure of the bond
from purely covalent, it introduces some ionic character
into the bond.

Polarization of ions represent the existence of some
covalent character in the ionic bonding.
Polarization of a covalent bond represents the existence
of some ionic character in the covalent bond.



IV. Bonding intermediate between ionic anc covalent Page 6


c) Factors affecting dipole moment

The dipole moment of a molecule is affected by
i. inductive effect – a substituent effect on an organic compound due to the permanent polarity or polarizability
of groups. This is transmitted through σ bond.
ii. mesomeric effect / resonance effect – delocalization of electron via π bond.
iii. presence of lone pair.

(1) Inductive effect (I)

This refers to the displacement of electron cloud mainly due to difference in electronegativity.
-I effect : electron withdrawing +I effect : electron donating

(2) Mesomeric effect / resonance effect (R)

This refers to the stabilization due to delocalization of electron through π bond..
-R effect : electron withdrawing +R effect : electron donating
For example, in benzenamine,
i. N is more electronegative than C and N exerts a -I effect.
ii. by resonance, lone pair on N is donated to the benzene ring and N exerts a +R effect.

NH
2
NH
2
NH
2

N
H
H

The final dipole moment would be the sum of the two effects.

N.B. Benzene ring can serves as a reservoir of electrons in resonance. If it is attached to a +R group, it will
behave as a -R group. On another hand, if it is attached to a -R group, it will behave as a +R group.

(3) Presence of lone pair

Lone pair can be considered as a negative centre and contributes a dipole moment.

For example, experimentally, NH
3
has a stronger dipole moment (1.46 D) than NF
3
(0.24D).

But
1. The difference in electronegativity between N(3.0) and F(4.0) is greater than that between N(3.0) and H(2.1).
2. The NF
3
has a bond angle smaller than NH
3
has.

According to these two factors only, NF
3
should has a stronger dipole moment than NH
3
.



But in NF
3
, the lone pair imposes a dipole moment opposing the dipole moment of N–F, this results in a much
weaker resultant dipole moment. Furthermore, the direction of the dipole moment cannot be determined because
we do not known which is stronger.
IV. Bonding intermediate between ionic anc covalent Page 7

Glossary
polarization of ion polarizing power polarizability Fajans rules electronegativity
Pauling scale dipole moment vector inductive effect mesomeric effect / resonance effect

Past Paper
Question
97 2A 1 a i ii iii
98 1A 1 c ii

97 2A 1 a i ii iii
1a i Explain the terms 'dipole' and 'dipole moment', using HBr as an example. 7
ii Explain why the dipole moment of HF is greater than that of HI.
iii State the effect of an electric field on molecules of the following compounds and explain the effect in terms of
dipole moment.
Cl
Cl

Cl
Cl



98 1A 1 c ii
1c The theoretical lattice enthalpies of NaCl
(s)
and AgCl
(s)
, and the experimental lattice enthalpy of AgCl
(s)
are given
in the table below.

Compound Theoretical lattice enthalpy Experimental enthalpy
NaCl
(s)
- 770 ?
AgCl
(s)
- 833 - 905
ii Why is there such a large difference between the theoretical and experimental lattice enthalpies of AgCl
(s)
? 1

V. Metallic bonding Page 1
Topic V. Metallic Bonding

Reference
Reading
4.9
Modern Physical Chemistry ELBS pg. 74–76
Chemistry in Context, 3rd Edition ELBS pg. 137
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 146–147
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 121–123

Syllabus
Metallic bonding
Electron Sea model
Delocalization model

Notes
V. Metallic bonding

A. Electron Sea model of metal


The metal atoms are closely packed (high coordination
number) to form a crystal lattice. Valence electrons of
individual atoms are contributed to form a sea of
electrons. The lattice of positive ions is then immersed
in the sea of electrons. The attraction arises from the
electrostatic attraction among the positive ions, mobile
electrons and positive ions.





General properties of metal

i. Thermal conductivity – the presence of mobile electrons
ii. Electrical conductivity – the presence of mobile electrons
iii. Malleability and ductility – non-directional electrostatic attraction between nuclei and mobile electrons
iv. Shiny lustre – The mobile electron is excited and re-emits the energy in form of lustre.

From another point of view, metallic bond may be considered an delocalization of valence electrons from each
atom over the entire metallic crystal.

(Further reading about band theory of metallic bonding can be found in Modern Physical Chemistry ELBS pg.
158–159)

B. Strength of metallic bond


Strength of a metallic bond depends on

i. packing efficiency of the crystal
Transition metal atoms are much smaller than the
atoms in Group 1A and 2A.

ii. availability of the valence electron
Group 1A metal has 1 valence e
-
. Group 2A metal
has 2 valence e
-
. Transition metal use 3d e
-
on top
of 2 4s e
-
.

iii. effective nuclear charge
In general, the metallic bond strength increases
with increasing effective nuclear charge on the
valence electrons. However, if the effective nuclear
charge is too high, this will lower the availability of
valence electrons and the bond strength will drop.
e.g. Hg has a first I.E. 10.44 V comparing with 5.14
V of Na.
V. Metallic bonding Page 2


C. Melting and boiling of metal

Upon melting, only small amount of the metallic bonds are broken. Majority of the metallic bond have to be
broken upon boiling. This causes a big gap between the melting point and boiling point of metal.
e.g. Na (371K/1156K), Fe (1809K/3135K)

In molecular substance, most of the attractions among the molecules have been broken upon melting. This results
in a smaller gap between the melting point and boiling point. e.g. N
2
(63K/77K), I
2
(387K/458K)

D. Strength of ionic bond, covalent bond and metallic bond

Estimated by Range (kJmol
-1
)
Ionic bond (non-directional) Lattice energy -780 (NaCl) – -3791(MgO)
Covalent bond (directional) Bond energy terms 158 (E(F–F)) – 945.4 (E(N≡N))
Metallic bond (non-directional) Atomization energy 107.3 (Na) – 514.2 (V)

Ionic bond
Covalent
Metallic
0 1000 2000 3000 4000 kJmol
-1

Glossary
malleability ductility lustre

Past Paper
Question
92 1A 2 d ii iii
98 1A 3 b i ii

92 1A 2 d ii iii
2d ii Describe the bonding in metallic crystals. 1½
‘Free electron’ model or ‘Mobile electron’ description. 1½ mark
iii Of the three energy ranges in kJmol
-1
given below:
5 - 100
200 - 700
800 - 1500,
which is the most likely energy range for the change M
(s)
→ M
(g)
, where M is a metal?
½
The best answer out of the three is 200-700 kJ mol
-1
. ½ mark

98 1A 3 b i ii
3b Sketch the trends for the properties mentioned in (i) and (ii) below, and account for the trend in each case.
i melting point of the alkali metals, Li, Na and K

2
ii boiling point of the Period 3 elements, Na, Mg and Al 2
V. Metallic bonding Page 3


Intermolecular forces
Intermolecular Forces

I. Van der Waals’ forces
A. Discovery of van der Waals' forces
B. Origin of van der Waals' forces
1. Induced dipole-induced dipole attractions
2. Dipole-dipole interactions
3. Dipole-induced dipole attractions
C. Relative strength of different origins of van der Waals' forces
II. Hydrogen bond
A. Nature
B. Strength
C. Solubility and hydrogen bond
D. Intramolecular hydrogen bond
E. Examples of hydrogen bonding
1. Ethanoic acid dimer
2. Simple hydrides - CH
4
, NH
3
, H
2
O and HF
3. Structure and physical properties of ice
4. Biochemical importance of hydrogen bond
a) DNA
b) Protein
F. Strength of van der Waals' forces and hydrogen bond
III. Relationship between structures and properties
I. Van der Waals' forces Page 1
Topic I. Van der Waals’ forces

Reference
Reading
4.10.1
Modern Physical Chemistry ELBS pg. 93–95
Chemistry in Context, 3rd Edition ELBS pg. 114–117
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 116–118
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 99–103

Syllabus
van der Waals' forces

Notes
Introduction to intermolecular forces and intramolecular forces

Study of chemistry can be divided into 2 main categories :

1. Chemical properties of substances (e.g. stability and reactivity)
These are depending on the intramolecular forces i.e. forces within a molecule – covalent bond.

2. Physical properties of substances (e.g. melting point, boiling point and solubility)
These are depending on the intermolecular forces i.e. forces among the molecule. e.g. van der Waals'' forces
and hydrogen bond.




There are two type of intermolecular
forces :

van der Waals'' forces and hydrogen
bond.
van der Waals'
forces
induced dipole-induced
dipole attractions
dipole-dipole
interactions
dipole-induced
dipole attractions
Hydrogen
bond
Intermolecular
forces

I. Van der Waals’ forces

A. Discovery of van der Waals' forces

van der Waals, Johannes Diderik (van der vals), 1837–1923, was a Dutch physicist. He discovered that real gas
doesn't obey ideal gas equation perfectly.

In ideal gas equation, it is assumed that there is no interaction among the gas molecules and the gas molecules
occupy no volume.

Ideal gas law : PV = nRT where P is the pressure measured
V is the volume measured
n is the number of mole of gas molecule
R is the universal gas constant
T is the temperature in Kelvin

Instead, the real gas follows another equation named after him, van der Waals' equation or real gas equation.

van der Waals' equation : ( P +
an
2
V
2 ) (V - nb) = nRT where a and b are called van der Waals' constant.

a is a measurement of the attraction among the particles and b is a measurement of the volume of the gas molecule.
I. Van der Waals' forces Page 2


The values of the empirical constants a and b are depending on the nature of the gas.

Gas a / atmdm
6
mol
-2
b / dm
3
mol
-1

He 0.0341 0.0237
N
2
1.39 0.0391
CO
2
3.63 0.0427
CH
3
CH
2
CH
2
CH
3
147 0.123

NH
3
4.19 0.0372

It can be seen that the attractions among the molecules and the size of the molecules increase from He to butane.

The weak forces of mutual attraction is called van der Waals forces.


B. Origin of van der Waals' forces

van der Waals' forces have 3 origins i. induced dipole-induced dipole attractions
ii. dipole-dipole (permanent dipole-permanent dipole) interactions
iii. dipole-induced dipole attractions


1. Induced dipole-induced dipole attractions

induced dipole-induced dipole attractions is a kind of
electrostatic attraction arises from fluctuation of
electron cloud.

Even at 0 K, electrons in a molecule are in constant
motion. Slight relative displacement of electrons in a
molecule will give rise to a temporary electrical dipole.
It will induce another temporary dipole on a
neighbouring molecule and an attractive force will be
established between the two.




Induced dipole-induced dipole attractions also has many other names

i. London force – it was first explained by scientist London in 1930.
ii. Dispersion force – it is caused by the unsymmetrical dispersion of electron cloud.
iv. Temporary induced dipole-temporary induced dipole attractions – dipole is not permanent.


Strength of induced dipole-induced dipole attractions depends on the polarizability of the electrons involved.

i. larger molecular size ⇒ larger electron cloud ⇒ higher polarizability ⇒ stronger induced dipole-
induced dipole attractions
A larger molecule means a larger electron cloud and higher polarizability, this gives strong induced dipole-
induced dipole attractions. In general, an unbranched molecule has a larger size than branched molecule.
Butane (b.p. -0.5ºC) has a higher boiling point than 2-methylpropane (b.p. -12ºC).

ii. small effective nuclear charge ⇒ more diffuse electron cloud ⇒ higher polarizability ⇒ stronger
induced dipole-induced dipole attractions
Fluorine is highly electronegative with high effective nuclear charge on the valence electrons.
CF
4
(m.m. 88) has a greater molecular mass than benzene (m.m. 78) but its boiling point (-128ºC) is lower
than that of benzene (80ºC).
Teflon, poly(tetrafluoroethene), is used to make the non-sticky surface of frying pan. The high
electronegativity, hence low polarizability of fluorine atom results in very small induced dipole-induced dipole
attractions.

I. Van der Waals' forces Page 3


2. Dipole-dipole interactions (permanent dipole-permanent dipole interactions)


There is dipole-dipole interactions among all polar
molecules. The oppositely charged ends tend to attract
each other and the similarly charged ends tend to repel
each other.

The molecules will arrange in a way with lowest
potential energy for the system. This means maximum
amount of attractions.



3. Dipole-induced dipole attractions

Like a temporary dipole, a polar molecule can also induce another temporary dipole on another molecule. The
attractions caused by this mean is called dipole-induced dipole attractions.

C. Relative strength of different origins of van der Waals' forces


Molecule induced dipole-induced
dipole attractions
dipole-dipole interactions
(permanent dipole-permanent
dipole interactions)
dipole-induced dipole
attractions

Ar (non-polar) 100 % nil nil

N
2
(non-polar) 100 % nil nil

CH
4
(non-polar) 100 % nil nil

CO (polar) ≈ 100 % 0.005 % 0.08 %

HCl (polar) 81 % 15 4 %


Although dipole-dipole interactions and dipole-induced dipole attractions are very weak comparing with induced
dipole-induced dipole attractions, polar molecule always has a higher m.p. and b.p. than a non-polar molecule with
comparable molecular mass. This is because on top of dipole-dipole interactions and dipole-induced dipole
attractions, there is always induced dipole-induced dipole attractions among polar molecules.

Glossary
van der Waals’ forces temporary dipole induced dipole-induced dipole attractions polarizability
dipole-dipole interactions dipole-induced dipole attractions

Past Paper
Question
91 2A 2 a
95 2B 4 a i
98 1A 1 b i

91 2A 2 a
2a Arrange the following substances in order of increasing boiling points: C
2
H
5
Cl, CH
4
and C
2
H
6
. Explain your
order by comparing the relative magnitudes and nature of the intermolecular forces.
4
CH
4
< C
2
H
6
< C
2
H
5
Cl 1 mark
C
2
H
5
Cl has one highly polarizable Cl atom and has a permanent dipole moment, while C
2
H
6
is less polarizable
than C
2
H
5
Cl and has no permanent dipole moment. Thus C
2
H
5
Cl is expected to have stronger intermolecular
forces than C
2
H
6
, and a higher boiling point. 1 mark
Both CH
4
and C
2
H
6
are non-polar but the molecular size and surface area of C
2
H
6
is larger than those of CH
4
, so
C
2
H
6
will have a stronger van der Waals’ forces. 2 marks


I. Van der Waals' forces Page 4
95 2B 4 a i
4a Explain the following facts:
i The boiling points of the halogens increase as the group is descended. 2
Boiling points of halogens depend on the strength of their intermolecular forces (van der Waal’s forces) which is
related to the strength of the instantaneous dipole of the molecule. 1 mark
Descending the group, with the increase in relative molecular size, the strength of the instantaneous dipole
increases. Hence more energy is needed for the boiling of the higher halogens. 1 mark


98 1A 1 b i
1b i An iodine molecule can be represented by the diagram below, with each dot '·' representing an atomic nucleus.

(I) Using one or more diagrams of this kind, illustrate your understanding of the two terms 'covalent radius' and
'van der Waals' radius'.
(II) Account for the difference between the covalent radius and van der Waals' radius for iodine.
2

II. Hydrogen bond Page 1
Topic II. Hydrogen bond

Reference
Reading
4.10.2
Modern Physical Chemistry ELBS pg. 90–92
Chemistry in Context, 3rd Edition ELBS pg. 117–126
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 118–123
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 103–112

Syllabus
Hydrogen bond
Strength of hydrogen bond
Intramolecular hydrogen bond

Notes
II. Hydrogen bond

A. Nature

Hydrogen bond can be considered as a kind of exceptionally strong dipole-dipole interactions.

When a hydrogen is bonded to a very electronegative element e.g. N, O and F, the bond pair electrons would be
attracted towards the latter one. The hydrogen atom without the bonding electron will become a naked proton.
It is then attracted by the lone pair of another very electronegative element.

H
F H
F
bond pair
very close to
the electronegative atom
naked proton
intermolecular hydrogen bond
δ
-
δ
-
δ
+
δ
+


Since the charge separation is large, this will give a strong dipole. The electrostatic attraction between the naked
proton and the lone pair is called hydrogen bond.

The size of proton, N, O and F are small, this facilitates close approach of two dipoles.


Necessary condition for the formation of hydrogen bond.
1. A hydrogen atom attaching to a very electronegative atom i.e. N, O, F.
2. A lone pair on a very electronegative atom i.e. N, O, F.




II. Hydrogen bond Page 2


B. Strength

i. Loneliness of the proton

If the hydrogen is bonded to a more electronegative atom, the covalent bond will be more polarized. This causes
the proton to be more isolated and the hydrogen bond would be stronger.

ii. Availability of the lone pair on the electronegative atom


C CH
3
CH
3
CH
3
OH

CH
3
CH
2
CH
2
CH
2
OH

2-methylpropan-2-ol pentan-1-ol
(b.p. 82.4 °C, m.p. 25.6 °C) (b.p. 138.1 °C, m.p. -78.9 °C)


Steric effect – If the lone pair is sterically hindered by bulky groups around it, it would be less available to form
hydrogen bond.


Though both melting point and boiling point are depending on the attraction among the particles, their value may
or may not parallel to each other.
e.g. 2-methylpropan-2-ol (b.p. 82.4 °C, m.p. 25.6 °C), pentan-1-ol (b.p. 138.1 °C, m.p. -78.9 °C)


Arrangement of particles Ordered Random Random
Attraction among the particles High Medium Low




C. Solubility and hydrogen bond

The solubility of the molecule is parallel to its ability to attract with the water molecule. In certain extent,
this is related to its ability to form hydrogen bond with water molecules.

N.B. The solubility is depending on the polarity rather than the size of the molecule. e.g. glucose (C
6
H
12
O
6
) is
soluble in water but methane (CH
4
) is insoluble in water.



II. Hydrogen bond Page 3


D. Intramolecular hydrogen bond

Besides intermolecular hydrogen bond, hydrogen bond may be formed within a single molecule, i.e. intramolecular
hydrogen bond.

Boiling point of nitrophenol :



O
H
N
O
O
-
+

N
O
O
O
H
-
+


N
O
O
O
H
-
+



2-nitrophenol (214ºC) 3-nitrophenol (290ºC) 4-nitrophenol (279ºC)


2-nitrophenol has lower boiling point and solubility than the other two isomer. Intramolecular hydrogen bond is
formed within the molecule. The intramolecular hydrogen bonding prevents formation of intermolecular bonding
hydrogen bond between molecules.
Intramolecular hydrogen bonding is impossible in 3- and 4-nitrophenol.


E. Examples of hydrogen bonding

1. Ethanoic acid

In gas phase or organic solvent, ethanoic acid dimerizes to form a dimer. The presence of an eight-membered ring
is confirmed by electron diffraction studies.
H
3
C C
O
O H
H
O
O
C CH
3

In aqueous solution, the molecules of a carboxylic acid link up with water molecules rather than form dimers.

2. Simple hydrides - CH
4
, NH
3
, H
2
O and HF

CH
4
NH
3
H
2
O HF
melting point (K) 91 195 273 190
boiling point (K) 109 240 373 293


There is no hydrogen bond among CH
4
molecule. 1 per molecule in NH
3

and HF. 2 per molecule in H
2
O.

Furthermore, boiling point is a better indicator of strength of hydrogen
bond than melting point because on top of attractions, melting process
involves breaking of crystal lattice. Therefore, melting point is also
depending on the packing of the crystal.

Consider the boiling point of group V, VI and VII hydrides. The boiling
point of the first member is much higher than the expected because of the
presence of hydrogen bond on top of van der Waals' forces.

The boiling points of group IV hydrides follow the general trend of
increasing boiling point with increasing molecular size. This is because of
the presence of van der Waals' forces only.
Boiling point of Group IV, V, VI and
VII hydrides
II. Hydrogen bond Page 4


3. Structure and physical properties of ice


Each water is capable to form two hydrogen bonds.
Including the two covalent bond, oxygen is
tetrahedrally coordinated.

In ice, the tetrahedrally coordinated oxygen atoms fit
into a nonplanar, six-membered ring of water molecules
associated through hydrogen bonding.



The ring structure extends in a 3-dimensional way. This
gives ice an open structure and lower density than
water.


When ice melts, the energy absorbed breaks some of the
intermolecular associations and the hexagonal crystal
lattice collapses. The density of water increases with
increasing temperature up to 4ºC as the hexagonal
structure continues to collapse.



4. Biochemical importance of hydrogen bond

a) DNA (Deoxyribonucleic acids)


Hydrogen bonding plays a crucial role in the
structures of many biochemical substances,
such as deoxyribonucleic acids (DNA).

The two helical nucleic acid chains are held
together by hydrogen bonds. These hydrogen
bonds are formed between specific pairs of
bases on the DNA chains, such as between the
adenine unit in one chain and a thymine unit in
the other; or between a guanine unit in one
chain and a cytosine unit in the other.
II. Hydrogen bond Page 5


b) Protein

Protein are made up from α-amino acid molecules. The –NH
2
group
condenses with –COOH group to form a peptide link, (
C N
O H
).
The polypeptide forms a helix structure with the amide groups joined together
by hydrogen bonds.

R
C H
2
N
H
C
O
OH C N C C N C C N C
O O O H
H
H
H H
H R R R

α-amino acid chain of polypeptide


F. Strength of van der Waals’ forces and hydrogen bond


H-bonds have the strength in the range 5–40 kJmol
-1
. van der Waals’ forces have roughly the same strength. For a
H-bonded molecule, there are both hydrogen bond and van der Waals’ force. Therefore, a H-bonded substance
always has a higher boiling point than those not H-bonded.
polar molecule
non-polar
molecule
molecule
with H-bond

induced-induced induced-induced induced-induced
dipole-dipole dipole-dipole
H-bond

Estimated by Range (kJmol
-1
)
Ionic bond (non-directional) Lattice energy -780 (NaCl) – -3791(MgO)
Covalent bond (directional) Bond energy terms 158 (E(F–F)) – 945.4 (E(N≡N))
Metallic bond (non-directional) Atomization energy 107.3 (Na) – 514.2 (V)

Comparing with ionic bond, covalent bond and metallic bond, both H-bond and van der Waals' forces are very
weak.

This explains why only 100ºC is required to boil water but 8000ºC is required to decompose water into hydrogen
and oxygen atoms.

O
H H
O
H H
O
H H
strong covalent
bond
weak hydrogen bond
and van der Waals' forces


Glossary
hydrogen bond steric effect intramolecular hydrogen bond open structure DNA
double helix structure amino acid peptide link amide group polypeptide

II. Hydrogen bond Page 6

Past Paper
Question
92 2B 6 Ac i 92 2B 6 Bc i 92 2C 7 d
93 1A 3 d
94 1A 2 d i ii iii 94 2A 2 b i 94 2B 4 b
97 1A 1 d i ii
98 1A 2 b 98 2B 6 a i
99 1A 1 b iii

92 2B 6 Ac i
6Ac
i Account for the difference in boiling points between NH
3
and PH
3
. 2
PH
3
molecules - van der Waals intermolecular forces 1 mark
NH
3
molecules - additional hydrogen bonding 1 mark


92 2B 6 Bc i
6Bc
i Account for the difference in boiling points between H
2
O and H
2
S. 2
Intermolecular hydrogen bonding in H
2
O but not H
2
S 1 mark
H
2
S van der Waals forces and permanent dipole-permanent dipole interactions only 1 mark


92 2C 7 d
7 A carboxylic acid P, with a relative molecular mass less than 100, contains C, 55.8%; H, 7.0%; and O, 37.2% by
mass . An attempt to convert P to its methyl ester Q by prolonged refluxing of P with methanol in the presence of
aqueous H
2
SO
4
gave the desired ester Q but with much of the starting material P unchanged.
(Relative atomic masses : H 1.0; C 12.0; O 16.0)

7d Which has a higher boiling point, the carboxylic acid or its methyl ester? Explain your answer. 3
Carboxylic acid has higher b.p. than its ester ½ mark
Hydrogen bonding 1 mark
R C
O
O
H
H
R C
O
O
or lone pair on oxygen bonded to acidic proton 1 mark
Need more energy to break off H-bonding. ∴higher b.p. ½ mark


93 1A 3 d
3d The boiling point and density of butan-1-ol are 117.9 ºC and 0.81 gcm
-3
respectively, and those of its isomer 2-
methylpropan-2-ol are 82.2 ºC and 0.79 gcm
-3
respectively. Account for these differences.
2
Alcohol molecules are held together by hydrogen bond. ½ mark
Methylpropan-2-ol is a tertiary alcohol and butan-1-ol is a primary alcohol. ½ mark
Due to steric interaction, 3º alcohol forms weaker intermolecular hydrogen bonds so its boiling point is lower.
1 mark
Further, the molecules are less closely packed and therefore results in lower density. ½ mark


94 1A 2 d i ii iii
2d i Explain the term “hydrogen bonding”. 2
H atom is situated between 2 small / electronegative atoms. 1 mark
One of these has a lone pair of electrons / bond energy in the range of 2 – 10 kJmol
-1
. 1 mark

ii Draw a diagram of the structure of a compound which has hydrogen bonds. Indicate the hydrogen bond(s)
clearly.
1
A actual example of intra / intermolecular hydrogen bond.
The example must show X–HLY or XLHLX 1 mark

iii Explain why
(I) the boiling point of CH
4
is lower than that of SiH
4
, and
(II) the boiling point of NH
3
is higher than that of PH
3
.
2
(I) Boiling points is expected to increase with number of electrons in the molecule (CH
4
→ SiH
4
) due to
increasing van der Waal’s forces. 1 mark
(II) Boiling point of NH
3
higher than the expected (i.e. >PH
3
) due to increased intermolecular attraction
(hydrogen bonding) 1 mark


II. Hydrogen bond Page 7
94 2A 2 b i
2b Account for each of the following:
i Concentrated H
3
PO
4
has a high viscosity. 2
In H
3
PO
4
, the intermolecular force is H-bond, ½ mark
and each H
3
PO
4
molecule is capable of forming 3 H-bonds with its neighbours. With strong intermolecular forces,
H
3
PO
4
has a high viscosity. 1 mark
P O O
O
O
H
H
H
½ mark


94 2B 4 b
4b Explain why hydrogen fluoride is a liquid at room temperature and atmospheric pressure while the other hydrogen
halides are gases.
2
The anomalous boiling point of HF is due to extensive H-bonding between HF molecules and other hydrogen
halides have no hydrogen bondings among the molecules. 1 mark
H
F
H
F
H
F
H
F
H
F
H
F
H
F

(diagram showing H-bonds in HF) 1 mark


97 1A 1 d i ii
1d Explain why 2
i the boiling point of HF is higher than that of HCl;
ii the boiling point of HI is higher than that of HBr.

98 1A 2 b
2b Which compound, H
2
O or F
2
O, would you expect to have a higher boiling point ? Explain your answer. 2

98 2B 6 a i
6a Consider the structures of the two synthetic polymers shown below.
HN(CH
2
)
6
NHCO(CH
2
)
4
CO
n
nylon-6.6
CH
2
CH
2
n
poly(ethene)



i Suggest an explanation for the fact that nylon-6,6 has a higher tensile strength than poly(ethene).

99 1A 1 b iii
1b Account for each of the following :
iii At 273 K, ice has a smaller density than water.

III. Relationship between structures and properties Page 1
Topic III. Relationship between structures and properties

Reference
Reading
4.0.1.0 4.11
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 109
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 402–403, 468–469

Syllabus
The relationship between structures and properties of materials

Notes
In chemistry, chemists intend to explain the chemical and physical properties of substances in term of particles and
the interaction among the particles.

All properties can be explained according to the following framework.

particles → attractions among particles → arrangement of particles → structure → properties


Example Particles Attractions among
particles
Arrangement
of particles
Structure Physical properties Chemical
properties
Zn
(s)
Zn atom strong metallic bond
due to delocalized
electron
hexagonal
close packing
giant
metallic
structure
high thermal and electrical
conductivities; hard; malleable;
ductile; dense; high m.p. & b.p.;
insoluble in any solvent except Hg
(l)
reducing
agent
Hg
(l)
Hg atom weak metallic bond
due to less
delocalized electron
random
arrangement in
liquid
liquid at
room
temperature
high thermal and electrical
conductivities;
relatively low m.p. & b.p.
very weak
reducing
agent
NaCl
(s)
Na
+
ion
& Cl
-
ion
strong ionic bond face centered
cubic
giant ionic
structure
low thermal and electrical
conductivities;
only conducts electricity in molten
state or aqueous state;
soluble in water
quite inert
AgCl
(s)
Ag
+
ion
& Cl
-
ion
ionic bond with very
strong covalent
character
cubic structure giant ionic
structure
low thermal and electrical
conductivities;
insoluble in water
quite inert
H
2
O
(l)
H
2
O
molecule
strong O–H covalent
bond and relatively
weak intermolecular
forces among
molecules
(Hydrogen bond and
van der Waals'
forces)
H
2
O is angular
in shape;
random
arrangement in
liquid; open
structure in ice
simple
molecular
structure /
molecular
crystal in
ice
low thermal and electrical
conductivities;
relatively low m.p. and b.p.;
high heat capacity
quite inert;
only
decomposes
into H and O
atom at
8000K
H
2(g)
H
2

molecule
strong H–H covalent
bond;
extremely weak
intermolecular
forces among
molecules (van der
Waals' forces only)
H–H is linear
in shape;
random
arrangement in
gas
simple
molecular
structure
low thermal and electrical
conductivities;
extremely low m.p. and b.p.;
low heat capacity
reducing
agent
III. Relationship between structures and properties Page 2

Example Particles Attractions among
particles
Arrangement
of particles
Structure Physical properties Chemical
properties
Graphite C atom strong covalent
bond with
delocalized
electrons between C
atoms;
weak van der Waals'
forces between
hexagonal layers
C atoms are
arranged in
hexagonal
layers with
large gap
between layers
giant
covalent
structure
high thermal and electrical
conductivities;
extremely high m.p. and b.p.;
brittle; insoluble in any solvent
reducing
agent
Diamond C atom strong covalent
bond between C
atoms
C atoms are
arranged
tetrahedral
network
giant
covalent
structure
low thermal and electrical
conductivities;
high m.p. and b.p.;
extremely hard;
insoluble in any solvent
reducing
agent
Glucose C
6
H
12
O
6

molecule
strong covalent
bond between C, H
and O;
weak intermolecular
forces among
molecules
glucose
molecule has a
ring structure
simple
molecule
structure
low thermal and electrical
conductivities;
moderate m.p. and b.p.;
soluble in water
chars upon
heating;
a weak
reducing
agent.

Glossary
particle bonding / attraction arrangement structure properties

III. Relationship between structures and properties Page 3

Past Paper
Question
90 2A 3 c
91 1A 2 d iii
93 2B 4 b iv
94 2C 9 b iv
99 1A 1 b i

90 2A 3 c
3c Arrange the following substances in order of increasing melting point: NaF, F
2
, HF. Explain your order in terms
of the bonding involved.
4
Melting involves the overcoming of forces between the units of which the solid is made. Two of the given solid
HF, F
2
would be expected to form molecular solids; the other, NaF would be expected to form ionic solid. The
coulombic forces holding an ionic solid together are strong, hence NaF would be expected to have high melting
point. 1 mark
The attraction between F
2
molecules is quite weak and due only to van der Waals forces would be expected to
have a low melting point. 1 mark
Even though HF forms molecular solid but because of the presence of hydrogen bonding between H and
neighbouring F atom, which can hold the molecules together more strongly and therefore, expected to have much
higher melting point than F
2
. 1 mark
F
2
(-219.6ºC) < HF(-89.1ºC) < NaF(993ºC) 1 mark


91 1A 2 d iii
2d iii Explain why the electrical conductivities of iron and of caesium chloride are different in the solid state. 1
In CsCl, the ions are held together by strong coulombic forces and cannot be easily displaced. Because of lack of
mobility of ions, conductivity is low. In iron, the iron atoms occupy the BCC sites and electrons are delocalized.
Conductivity is high because electrons can move. 1 mark


93 2B 4 b iv
4b Account for each of the following facts:
iv There is a significant difference in the melting point between silicon (m.p. 1410 ºC) and lead (m.p. 328 ºC). 2
Silicon has a giant covalent network structure. C.N. = 4
Lead has a close packed metallic structure. C.N. = 12 1 mark
The Si–Si in silicon is strong compared with the metallic bond in lead and in the liquid state of lead is residual
metallic bond remained. ∴ silicon has a higher melting point than lead. 1 mark


94 2C 9 b iv
9b Ethene and chloroethene can undergo polymerization to give polyethene (PE) and polyvinyl chloride (PVC)
respectively. PVC is more rigid and durable than PE, but incineration of PVC causes a more serious pollution
problem.

iv Explain why PVC is more rigid than PE. 1
The structure of PVC can be represented by

The attraction between polymer chains of PVC is dipolar attraction while that between PE polymer is van der
Waal's force which is weaker when compared with the former. Hence PVC is more rigid and more durable than
PE. 1 mark


99 1A 1 b i
1b Account for each of the following :
i At 298 K and 1 atm pressure, carbon dioxide is a gas whereas silicon dioxide is a solid.


States of Matter

I. Solid state
A. Metallic structure
1. Hexagonal close packing
2. Cubic close packing - face centred cubic
3. Tetrahedral holes and octahedral holes
4. Body-centred cubic structure
B. Giant ionic structure
C. Covalent giant structure
1. Allotrope of carbon
a) Diamond
b) Graphite
2. Silicon(IV) oxide
D. Molecular crystal
1. Iodine – face centred cubic
2. Carbon dioxide (Dry ice) – face centred cubic

II. Gaseous state
A. Gas laws
1. Charles' law
2. Boyle's law
3. Avogadro's law
4. PVT surface
B. Ideal gas equation (Ideal gas law)
1. Molar volume
C. Determination of molecular mass
1. Experimental determination of molar mass of a gas
2. Experimental determination of molar mass of a volatile liquid
D. Dalton's law of partial pressure
1. Mole fraction
2. Relationship between partial pressure and mole fraction
I. Solid State Unit 1 Page 1
Topic I. Solid state Unit 1

Reference
Reading
4.12.1
Modern Physical Chemistry ELBS pg. 154–155
Chemistry in Context, 3rd Edition ELBS pg. 134–136
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 147–149
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 45, 119–121

Syllabus
Close packing structure
Body centred cubic structure

Notes
I. Solid state

A. Metallic structure

In metal crystal, the metal atoms tends to pack with each other closely and has a high coordination no.

Coordination no. – the number of atoms closest to a particular atom.

There are two kinds of close packing - hexagonal close packing and cubic close packing.

1. Hexagonal close packing (74% of the space is filled)

Some of the metal have hexagonal close packing (h.c.p.). e.g. Cobalt, Titanium and Zinc


In hexagonal close packing, each atom is surrounded by 12 atoms, i.e.
coordination is 12. 6 on the same layer, 3 on the top and 3 at the bottom.
Since the orientation of the first and third layer are the same, this is also
called abab... pattern.
Unit cell – smallest portion of the crystal which contains all the
fundamentals (information) without repetition.

No. of atoms in an unit cell
12 at the corner 12 ×
1
6
= 2
2 on the face 2 ×
1
2
= 1
3 in the cell 3 × 1 = 3

Total no. of atoms in an unit cell = 6

I. Solid State Unit 1 Page 2


2. Cubic close packing - face centred cubic (74% of the space is filled)

Cubic close packing (c.c.p.) is also called face centre cubic packing (f.c.c.). Examples are Copper, Nickel and
Calcium


The coordination no. of any atom in the structure is also 12. The first layer
has a different orientation with the third layer of atoms. This is called
abcabc... pattern.

By looking at a four layers unit cell, 1 atom at the first layer, 6 at the second
layer, 6 at the third layer and 1 at the fourth layer, a face centred cubic unit
cell can be constructed.
No. of atoms in an unit cell
8 at the corner 8 ×
1
8
= 1
6 on the face 6 ×
1
2
= 3

Total no. of atoms in an unit cell = 4


I. Solid State Unit 1 Page 3


3. Tetrahedral holes and octahedral holes

Although the crystal is closely packed, there is still some spaces between the atoms. They are called holes. There
are two types of holes – tetrahedral hole and octahedral hole



Octahedral hole

Octahedral hole is surrounded by 6 atoms. It is the space between two
layers of triangularly arranged atoms. From another angle, it can be seen
that the six atoms are arranged in a form of octahedron.




Tetrahedral hole

Tetrahedral hole is surround by 4 atoms. The four atoms are arranged in a
form of tetrahedron. It has a smaller size than octahedral hole.



4. Body-centred cubic structure (68% of the space is filled)

e.g. Sodium, Potassium and Chromium

Body-centred cubic (b.c.c.) structure is not a close packing structure. Only
68% of the space is filled comparing with 74% in the two close packing
structures.

In body-centred cubic structure, the coordination no. of any atom is 8.

No. of atoms in an unit cell
8 at the corner 8 ×
1
8
= 1
1 at the centre 1 × 1 = 1

Total no. of atoms in an unit cell = 2


Glossary
coordination no. hexagonal close packing cubic close packing face centred cubic
tetrahedral hole octahedral hole body centred cubic unit cell

I. Solid State Unit 1 Page 4

Past Paper
Question
90 1A 2 c
91 1A 2 d i
92 1A 2 d i
97 1A 1 a i ii

90 1A 2 c
2c Compare and contrast the two close packing atomic arrangements in metals. 3
Metals having the hexagonal close packing has the abab... arrangement for atoms in different layers. Metals
having the face-centred cubic close packing has the abcabc... arrangement for atoms in different layers. 2 marks
Both arrangements have the same packing efficiency. or 1 mark
Atoms in both close packing arrangements all have the co-ordination number of 12.


91 1A 2 d i
2d i Iron has a body-centred structure. Draw a unit cell representation of iron. 1

1 mark


92 1A 2 d i
2d The arrangement of atoms in metals can be described by the close-packing of spheres.
i Which close-packed structure does abcabcabc... describe?
Indicate on the diagram below one tetrahedral hole (marking it T) and one octahedral hole (marking it O).



Cubic closest packed structure. ½ mark
½ mark for O and ½ mark for T


97 1A 1 a i ii
1a At room temperature, iron has a body-centred cubic structure. 2
i Draw the unit cell representation of iron.
ii Deduce the number of atoms in one unit cell of iron.

I. Solid state Unit 2 Page 1
Topic I. Solid state Unit 2

Reference
Reading
4.12.2
Modern Physical Chemistry ELBS pg. 159–162, 165–166
Chemistry in Context, 3rd Edition ELBS pg. 138–146
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 149–151
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 124–126

Syllabus
Giant ionic structure


Notes
B. Giant ionic structure

Ionic crystal is the result of a balance between attractions and repulsions.

If the attraction forces and the repulsion forces are not balanced, the structure will be unstable. The ions will be
rearranged and another more stable structure will be resulted. This depends on the relative size of the ions in the
ionic crystal.






Stable Limiting radius Unstable Stable

The arrangement of the ions in an ionic crystal is determined by the ionic radii ratio (r
+
/r
-
):

Coordination no. Shape r
+
/r
-
Example
8 Simple cubic 0.73 and above CsCl
6 Face centered cubic (Octahedral) 0.41 - 0.73 NaCl
4 Face-centered cubic (Tetrahedral) 0.22 - 0.41 ZnS





Caesium chloride
Simple cubic
Sodium chloride
face-centred cubic (octahedral)
Zinc blende (Zinc sulphide)
face centred cubic (tetrahedral)

Cs
+
ions occupy the centre of the
cubes formed by 8 Cl
-
ions
Na
+
ions occupy the octahedral
holes formed by 6 Cl
-
ions
Zn
2+
ions occupy half of the
tetrahedral holes formed by 4 S
2-
ion

no. of Cs
+
ions in the unit cell
1 at the centre 1 × 1 = 1
Total no. of Cs
+
ions = 1

no. of Cl
-
ions in the unit cell
4 at the corner 4 ×
1
4
= 1
Total no. of Cl
-
ions = 1
no. of Na
+
ions in the unit cell
1 at the centre 1 × 1 = 1
12 on the edge 12 ×
1
4
= 3
Total no. of Na
+
ions = 4

no. of Cl
-
ions in the unit cell
6 on the face 6 ×
1
2
= 3
8 at the corner 8 ×
1
8
= 1
Total no. of Cl
-
ions = 4
no. of Zn
2+
ions in the unit cell
4 in the cell 4 × 1 = 4
Total no. of Zn
2+
ions = 4

no. of S
2-
ions in the unit cell
6 on the face 6 ×
1
2
= 3
8 at the corner 8 ×
1
8
= 1
Total no. of S
2-
ions = 4

Coordination no. of Cs
+
ion = 8
Coordination no. of Cl
-
ion = 8
Coordination no. of Na
+
ion = 6
Coordination no. of Cl
-
ion = 6
Coordination no. of Zn
2+
ion = 4
Coordination no. of S
2-
ion = 4
I. Solid state Unit 2 Page 2


Both the no. of ions in the unit cell and ratio of coordination no. can be used to determine the empirical formula of
the ionic compound.


The structure of an ionic crystal is labeled according to the positions of the formula units, not the position of
individual ions. The position of each formula unit is called a lattice point.

Take CsCl as the example, consider each pair of Cs
+
ion and Cl
-
ion as a lattice point. The lattice points are
arranged in a simple cubic manner i.e. 8 lattice point occupy the 8 corners of a cube.

Glossary
giant ionic structure zinc blende

Past Paper
Question
94 1A 1 b i ii
99 2A 2 c i ii

94 1A 1 b i ii
1b The crystal structure of a compound A
x
B
y
can be described as a simple cubic lattice of A atoms with B atoms at
the middle of all the edges.

i What is the empirical formula of this compound? 1

No. of atom A per unit-cell = 8 ×
1
8
= 1
No. of atom B per unit-cell = 12 ×
1
4
= 3
∴ Empirical formula of the compound is AB
3
. 1 mark

ii What are the coordination numbers of an A atom and a B atom respectively? 1
Coordination number of A = 6 ½ mark
Coordination number of B = 2 ½ mark


99 2A 2 c i ii
2c i Consider the unit cell of calcium fluoride shown below:

(I) State the respective coordination numbers of each calcium ion and each fluoride ion.
(II) Describe the lattice of calcium ions and that of fluoride ions.

ii (I) Draw the unit cell of caesium chloride.
(II) Describe the lattice of caesium ions and that of chloride ions in caesium chloride.


I. Solid state Unit 3 Page 1
Topic I. Solid state Unit 3

Reference
Reading
4.12.3
Modern Physical Chemistry ELBS pg. 159–162, 165–166
Chemistry in Context, 3rd Edition ELBS pg. 138–146
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 152–154
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 46, 123–124

Syllabus
Giant covalent structure

Notes
C. Giant covalent structure


1. Allotrope of carbon

Allotropy – The existence of more than one physical form of the element in the same state. e.g. graphite and
diamond, red phosphorus and white phosphorus, oxygen and ozone.

Carbon has two common allotropes – graphite and diamond. The two allotropes have different physical properties
but similar chemical properties. This can be explained by the structures of the two allotropes.

Properties Diamond Graphite
appearance colourless, transparent crystal black, shiny solid
hardness hardest natural substance known brittle
density 3.5 gcm
-3
2.2 gcm
-3

electrical conductivity does not conduct conducts in one direction
melting point 3550 ºC 3730 ºC


a) Diamond


Each carbon is sp
3
hybridized. The sp
3
hybrid orbitals are overlapped to
form strong σ covalent bond ⇒ hard, high density, high melting point and
boiling point.

The bonding is extended to form a 3-dimensional network.




b) Graphite


Each carbon is sp
2
hybridized. The sp
2
hybrid orbitals are overlapped to
form strong σ covalent bond. The p orbitals perpendicular to the carbon
layer are overlapped to form π bond. ⇒ higher melting point than diamond.

This gives a hexagonal layer structure. There are only weak van der Waals’
forces between the layers. ⇒ brittle and low density

The π electrons are delocalization above and below the layer in a direction
parallel to the layer. ⇒ conducts electricity in one direction, shiny
appearance

I. Solid state Unit 3 Page 2


2. Silicon(IV) oxide


Quartz / Sand / silicon(IV) oxide / silicon oxide / silicon dioxide (SiO
2
)


The structure of quartz is similar to that of diamond.

Each silicon atom is joined to 4 oxygen atoms and each
oxygen atom is then connected to another silicon atom.

The silicon and oxygen are joined together by strong
covalent bond. Upon melting, a lot of energy is required
to break the Si–O covalent bond. Therefore, silicon(IV)
oxide has a relatively high melting point 1610ºC.


Glossary
allotrope hexagonal layer structure


Past Paper
Question
90 2B 4 b
92 2A 3 a i ii
98 2A 2 a i ii

90 2B 4 b
4 Account for the following observations.
4b SiO
2
is a solid with a high melting point, whereas CO
2
is a gas at room temperature. 4
SiO
2
- three dimensional polymeric solid with very strong Si-O bonds.
(Si-O bond must be stated; with strong bonds only - 0 mark) 2 marks
CO
2
- exists as discrete molecules with only weak intermolecular van der Waals’ forces. 2 marks


92 2A 3 a i ii
3a i Describe the bonding and intermolecular forces in ice and in SiO
2
solid. 2
Ice consists of covalent H
2
O molecules held together by hydrogen bonding.
Quartz, SiO
2
solid, is an infinite three dimensional network(giant structure) solid in which each Si atom is
covalently bonded in a tetrahedral arrangement to four O atoms. 2 marks

ii What type of interactions must be overcome to melt these solid? 2
Hydrogen bonding must be overcome in order to melt ice. In order for SiO
2(s)
to melt, some of the strong Si-O
covalent bonds have to be broken. 2 marks


98 2A 2 a i ii
2a The structures of the two allotropes of carbon, diamond and graphite, are shown below.

6
i Comment on the three different carbon-carbon distances as indicated in the above structures.
ii With reference to the above structures, explain why diamond is hard whereas graphite is soft enough to be used as
lubricant.


I. Solid state Unit 4 Page 1
Topic I. Solid state Unit 4

Reference
Reading
4.12.4
Modern Physical Chemistry ELBS pg. 159–162, 165–166
Chemistry in Context, 3rd Edition ELBS pg. 138–146
Physical Chemistry, Fillans pg. 212–220
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 151–152
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 47, 130–132

Syllabus
Molecular crystal

Notes


D. Molecular crystal

Molecular crystal consists of molecules held in lattice sites by weak intermolecular forces such as van der Waals’
forces or hydrogen bonds. The structure of molecular crystals are determined by the shape of the basic molecular
units which tend to pack together as efficient as possible.


1. Iodine – face centred cubic


2. Carbon dioxide (Dry ice) - face centred cubic




Glossary
molecular crystal

Past Paper
Question



II. Gaseous state Unit 1 Page 1
Topic II. Gaseous state Unit 1

Reference
Reading

0.5.3.1–0.5.3.2
ILPAC 9 (2nd ed.), John Murray, pg 7–19
Modern Physical Chemistry (4th ed.), Bell & Hyman Ltd., pg 143–144
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., pg 155

Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., pg 163–165, 167
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 137–139

Syllabus
Charles' law
Molar volume
Boyle's law
Avogadro's law
Ideal gas equation (Ideal gas law)
Molar volume of gases

Notes
II. Gaseous state

A. Gas Laws

1. Charles’ Law

For a given mass of gas, the volume is directly proportional to the absolute temperature (Kelvin scale) at a given
pressure. V ∝ T


2. Boyle’s Law


For a given mass of gas, the volume is inversely proportional to the pressure at
a given temperature. V ∝
1
P





3. Avogadro’s Law

At constant pressure and temperature, the volume of a gas is directly proportional to the number of gaseous
particle.

V ∝ N or V ∝ n N : no. of particle, n : no. of mole of particle

II. Gaseous state Unit 1 Page 2


4 PVT surface

PVT relationship of an ideal gas can be represented by a
2-dimensional surface.

PVT surface for an ideal gas



B. Ideal gas equation (Ideal gas law)

By combining the three gas laws, an ideal gas equation can be derived.

By combining V ∝ T, V ∝
1
P
and V ∝ n ⇒ V ∝
nT
P


Therefore,
PV
nT
= constant

The constant is called gas constant, R and the relationship becomes PV = nRT

Unit
P : 1 atm = 101325 Nm
-2
(Pa)

= 760 mmHg
V : 1 m
3
= 1000 dm
3
= 1000000 cm
3

n : no. of mole
T : must be in Kelvin (K)
R : 8.314 JK
-1
mol
-1
= 82.05 cm
3
atmK
-1
mol
-1


II. Gaseous state Unit 1 Page 3


1. Molar volume


Since the volume occupied by a gas is mainly space whose size is depending on the
motion of the particles only, all gases have the similar molar volume. i.e. the molar
volume is independent of the nature of the particles.

It is found that the molar volume of any gas at 0 ºC (273 K) and 1 atm is about 22.4
dm
3
.

The condition 0 ºC and 1 atm is called standard temperature and pressure (stp) or
standard condition.

Gas Formula Molar volume at stp, V
m
/ dm
3
mol
-1

Helium He 22.396
Hydrogen H
2
22.432
Carbon dioxide CO
2
22.262




By using the ideal gas equation, the molar volume of a gas at different condition can also be determined.

For example, the condition 25ºC (273K) and 1 atm is called room temperature and pressure (rtp) or room
condition. The molar volume at stp can be determined by using ideal gas equation.

PV = nRT

P
1
V
1
n
1
T
1
=
P
2
V
2
n
2
T
2


1 atm × 22.4 dm
3
1 mole × 273 K
=
1 atm × V
2
1 mole × 298 K


V
2
= 24.5 dm
3


Since the value is only an approximate value, usually the molar volume of a gas is assumed to be
24 dm
3
at rtp.

Glossary
Charles' law absolute temperature (Kelvin scale) Boyle's law Avogadro's law PVT surface
ideal gas equation gas constant / universal gas constant molar volume
standard temperature and pressure (stp) / standard condition
room temperature and pressure (rtp) / room condition

Past Paper
Question
94 2A 1 a i

94 2A 1 a i
1a Gas container A and B each contain an ideal gas at low pressure and 298 K. The volume of container A is twice
that of container B, but the number of moles of ideal gas contained in A is only half of that in B.

i Calculate the ratio of the gas pressure in the two containers. 3
P
A
V
A
= n
A
RT
P
B
V
B
= n
B
RT 1 mark
P
A
P
B
=
n
A
n
B
(
V
B
V
A
) 1 mark
=
1
2
(
1
2
) =
1
4

P
A
=
1
4
P
B
or P
B
= 4P
A
1 mark


II. Gaseous State Unit 2 Page 1
Topic II. Gaseous State Unit 2

Reference
Reading
0.5.3.3
ILPAC 9 (2nd ed.), John Murray, pg 21–25
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., pg 158–160
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 143–144

Assignment
Reading

A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 168, 180–181

Syllabus
Determination of molecular mass

Notes
C. Determination of molecular mass

Although molecular mass of a substance is a microscopic properties which cannot be measured directly, ideal gas
equation provides a link between molecular mass of a gas and some measurable quantities.


PV = nRT where P is the pressure of the gas
V is the volume of the gas
n is the number of mole of gaseous particle
R is the gas constant
T is the temperature in Kelvin

The quantity of no. of mole is related to the molar mass by the relationship, n =
m
M
m
, where m is the mass of the
gas and M
m
is the molar mass of the gas. Since molar mass is numerically the same as molecular mass, molecular
mass can be determined by measuring the mass, pressure, volume and temperature of a gas.


PV = nRT

PV =
m
M
m
(RT) where m is the mass of the gas
M
m
is the molar mass of the gas

M
m
=
m
PV
(RT) or M
m
=
ρ
P
(RT) where, ρ is the density of the gas =
m
V


II. Gaseous State Unit 2 Page 2


1. Experimental determination of molar mass of a gas

By determining the mass, pressure, volume and temperature of a gas (e.g. CO
2(g)
), the molar mass of the gas can be
determined. In the following experiment, a volumetric flask is used to measure the volume and the mass of the gas.

Measured values
Mass of volumetric flask filled with air = 47.993 g
Mass of volumetric flask filled with CO
2
= 47.998 g
Mass of volumetric flask filled with water = 152.8 g
Room temperature = 26 ºC
Atmospheric pressure = 757 mmHg

Given values
Density of water at 26ºC = 1.00 gcm
-3

Density of air at 26ºC and 757 mmHg = 0.00118 gcm
-3

Gas constant (R) = 0.0821 atmdm
3
K
-1
mol
-1



Calculation

Molar Mass of CO
2
=
mass of CO
2
× gas constant × temp. in K
pressure of CO
2
× volume of CO
2
=
mRT
PV


Note ! Your should keep all the units in the intermediate steps.


Mass of CO
2


Mass of water = Mass of volumetric flask filled with water - Mass of volumetric flask (filled with air)
(the mass of air is neglected in this step)
= 152.8 g - 47.933 g = 104.9 g

Volume of the flask =
mass of water
density of water
=
104.9 g
1.00 gcm
-3 = 104.9 cm
3


Mass of air = Volume of flask × density of air = 104.9 cm
3
× 0.00118 gcm
-3
= 0.124 g

Mass of empty volumetric flask = Mass of volumetric flask filled with air - Mass of air
= 47.933 g - 0.124 g = 47.809 g

Mass of CO
2
= mass of volumetric flask filled with CO
2
- mass of empty volumetric flask
= 47.998 g - 47.809 g = 0.189 g

Pressure of CO
2
= atmospheric pressure

Volume of CO
2
= volume of the flask


Molar Mass of CO
2
=
mass of CO
2
× gas constant × temp. in K
pressure of CO
2
× volume of CO
2
=
mRT
PV


=
0.189 g × 0.0821 atmdm
3
K
-1
mol
-1
× (273 + 26)K
757
760
atm ×
105.0
1000
dm
3
= 44.4 gmol
-1


II. Gaseous State Unit 2 Page 3


2. Experimental determination of molar mass of a volatile liquid

The molar mass of a volatile liquid cannot be determined directly according to ideal gas equation, the liquid must
be vaporized first. By injecting a known mass of volatile liquid into a heated gas syringe, the molar mass of the
volatile liquid can be determined using the ideal gas equation.

Molar Mass of the volatile liquid =
mass of the liquid × gas constant × temp. in K
pressure of the vapour × volume of the vapour


=
mRT
PV


The mass of the liquid is measured by a hypodermic syringe and a balance. It is determined by comparing the mass
of the hypodermic syringe before and after injection.


The hypodermic needle is equipped with a self-sealing rubber to ensure no loss of vapour from the gas syringe.




The volume of the vapour is measured by the volume displaced by the vapour in the heated gas syringe.

Precautions : 1. The needle of hypodermic syringe must be long enough to inject the liquid into the inner part
of gas syringe where the temperature is higher. This ensures complete vaporization of liquid.
2. The temperature and volume readings must become steady before any record is taken.
3. To ensure accurate injection of liquid, the hypodermic syringe should be rinsed with the
liquid first and any bubbles in the syringe should be expelled. Keep the syringe horizontal
and avoid touching the piston or warming the barrel with you hand, either of which could
result in loss of liquid.

II. Gaseous State Unit 2 Page 4


Measured values
Mass of hypodermic syringe and liquid before injection = 13.189 g
Mass of hypodermic syringe and liquid after injection = 12.920 g
Temperature of the vapour = 100 ºC
Atmospheric pressure = 762 mmHg
Volume of air in gas syringe before injection = 5.0 cm
3

Volume of air and vapour in gas syringe after injection = 66.0 cm
3


Given values
Gas constant (R) = 0.0821 atmdm
3
K
-1
mol
-1

1 atm = 760 mmHg

Calculation
PV = nRT =
m
M
m
RT

762
760
atm × (
66.0 - 5.0
1000
dm
3
) =
(13.189 -12.920 g)
M
m
× 0.0821 atmdm
3
K
-1
mol
-1
× (100 + 273) K

M
m
= 135 gmol
-1

Mass of liquid used = mass of hypodermic syringe before injection - mass of hypodermic syringe after injection
= 13.189 g - 12.920 g = 0.269 g

Temperature of vapour = temperature of the steam jacket = 100 ºC = 373 K

Pressure of vapour = atmospheric pressure =
762
760
atm = 1.00 atm

Volume of vapour = Volume of air and vapour in gas syringe - Volume of air in gas syringe
= 66.0 cm
3
- 5.0 cm
3
= 61.0 cm
3
= 0.0610 dm
3



Molar Mass of the volatile liquid =
mass of the liquid × gas constant × temp. in K
pressure of the vapour × volume of the vapour
=
mRT
PV


=
0.269 g × 0.0821 atmdm
3
K
-1
mol
-1
× 373 K
1.00 atm × 0.0610 dm
3 = 135 gmol
-1



Glossary

molar mass gas syringe hypodermic syringe self-sealing rubber steam jacket

Past Paper
Question
95 2A 3 a i
97 2A 1 b
99 1A 1 a i ii

95 2A 3 a i
3a i Derive an expression for the molar mass M of an ideal gas, in terms of its density d, pressure P, and absolute
temperature T.
2
PV = nRT ½ mark
n =
m
M
where m is the mass of dry air ½ mark
PV =
m
M
(RT)
M =
m
PV
(RT) =
d
P
(RT) 1 mark

C i Generally well answered. However, some candidates did not express M in terms of d, P and T explicitly.

97 2A 1 b
1b At 360 K and 101 kPa pressure, the vapour produced by 0.226 g of a volatile liquid occupies 85.0 cm
3
. Assuming
that the vapor behaves ideally, calculate the molar mass of the liquid.
(1 kPa = 1 × 10
3
Nm
-2
) (Gas constant, R = 8.31 JK
-1
mol
-1
)


II. Gaseous State Unit 2 Page 5
99 1A 1 a i ii
1a At 433 K, 0.569 g of aluminium chloride produces a vapour having a volume of 96.0 cm
3
and a pressure of 80.0
kPa.

i Assuming that the aluminium chloride vapour behaves as an ideal gas, calculate its molar mass.
(1 kPa = 1 × 10
3
Nm
-2
)

ii Deduce the molecular formula of aluminium chloride under the above conditions and suggest a structure
consistent with this formula.


II. Gaseous State Unit 3 Page 1
Topic II. Gaseous State Unit 3

Reference
Reading

4.13.4
ILPAC 9 (2nd ed.), John Murray, pg 33–34
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., pg 156
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 140

Assignment
Reading

A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 169
Syllabus
Dalton's law of partial pressure
Relationship between partial pressure and mole fraction

Notes
D. Dalton’s law of partial pressure


Dalton’s law of partial pressure –

The total pressure (P
Total
) exerted by a mixture of gases is equal to the sum of the
partial pressure (p) of each constituent gas.


P
Total
= p
1
+ p
2
+ p
3
...p
n



The partial pressure is defined as the pressure the gas would exert if it was contained in the same volume as that
occupied by the mixture.



1. Mole fraction

Mole fraction is the percentage of a particular component in a mixture in term of number.

e.g. For a mixture containing 0.2 mole of oxygen, 0.3 mole of hydrogen and 0.3 mole of carbon dioxide, the mole
fraction oxygen in the mixture can be calculated by

mole fraction of oxygen =
no. of mole of oxygen molecules
total no. of mole of molecules
=
0.2
0.2 + 0.3 + 0.3
= 0.25

It is different from percentage by mass. In the above example, 0.2 mole of oxygen weighs 6.4 g, 0.3 mole of
hydrogen weighs 0.6 g and 0.3 mole of carbon dioxide weighs 13.2 g.

Percentage by mass of oxygen =
mass of oxygen
total mass
=
6.4 g
6.4 g + 0.6 g + 13.2 g
= 0.32 = 32%
II. Gaseous State Unit 3 Page 2


2. Relationship between partial pressure and mole fraction

According to the ideal gas equation, the pressure of a gas is directly proportional to the no. of gaseous particle or
the no. of mole of particle present.
P ∝ N or P ∝ n where N is the total no. and n is the no. of mole,
they are related by the expression N = nL where L is Avogadro's constant.

By combining with Dalton's law of partial pressure, the partial pressure exhibited by individual component in a
gaseous mixture should also be proportional to the no. of mole of that kind of particle.

1 : P
T
∝ n where P
T
is the total pressure and n is the total no. of mole of particles.
2 : p
i
∝ n
i
p
i
is the partial pressure of a component and n
i
is the no. of mole of that component

Combining 1 & 2,
p
i
P
T
=
n
i
n
= mole fraction of individual component in the mixture

The mole fraction of individual component can be calculated from the partial pressure p
i
and the total pressure P
T
.

Glossary
Dalton's law of partial pressure partial pressure mole fraction percentage by mass

Past Paper
Question
91 1A 2c
95 2A 3 a ii
96 2A 2 a ii

91 1A 2c
2c A container holds a gaseous mixture of nitrogen and propane. The pressure in the container at 200ºC is 4.5 atm.
At -40ºC the propane completely condenses and the pressure drops to 1.5 atm. Calculate the mole fraction of
propane in the original gaseous mixture.
3
n
t
RT
1
= P
1
V
1
(1)
n
t
(1 - x)RT
2
= P
2
V
1
(2)
where n
t
is total number of moles, x is mole fraction of propane
(2) ÷ (1)
(1 - x)
T
2
T
1
=
P
2
P
1
(1 - x) =
1.5
4.5
·
473.15
233.15
= 0.067646 x = 0.3235
1 mark for correct final answer (0.315 - 0.324)
2 marks for intermediate answers (partial pressure, partial volume, no. of mole), equations and method.


95 2A 3 a ii
3a ii At 98.6 kPa and 300 K, the density of a sample of dry air is 1.146 g dm
-3
. Assuming that dry air contains only
nitrogen and oxygen and behaves ideally, calculate the composition of the sample.
(Gas constant, R = 8.31 J K
-1
mol
-1
)
3
Molar mass of dry air
=
1.146 gdm
-3
98.6 kPa
× 8.31 JK
-1
mol
-1
× 300 K =
1.146 × 10
3
gm
-3
98.6 × 10
3
Nm
-2 × 8.31 JK
-1
mol
-1
× 300 K = 28.98 gmol
-1
1 mark
Let mole fraction of N
2
be x
28.02 x + 32.0 (1 - x) = 28.98 1 mark
x = 0.759
Composition of dry air
75.9% N
2
and 24.1% O
2
1 mark

C ii A number of candidates made mistakes in the numerical calculation and in the units used.

96 2A 2 a ii
2a ii At 298 K 1.0 dm
3
of N
2
at 0.20 Pa pressure was mixed with 2.0 dm
3
of O
2
at 0.40 Pa in a 4.0 dm
3
container.
Assuming that both N
2
and O
2
behave ideally, calculate the pressure of the gaseous mixture at 298 K.
2
In the mixture
partial pressure of N
2
= ¼ × 0.20 Pa = 0.05 Pa ½ mark
partial pressure of O
2
= ½ × 0.40 Pa = 0.20 Pa ½ mark
pressure of mixture = (0.05 + 0.20) Pa = 0.25 Pa 1 mark


Chemical Kinetics Page 1
Chemical Kinetics

I. Rates of chemical reactions
A. Definition of rate of reaction
1. Unit of rate of reaction
B. Measuring the rate of reaction
1. Different approaches
a) Constant amount approach
b) Constant time approach
2. Interpretation of physical measurements made in following a reaction
a) Volume of gas formed
b) Colorimetric measurement
II. Order of reaction
A. Rate Law or rate equation
1. Differential form and integrated form of rate law
2. Graphical presentation of reaction rate
3. Order of reaction
a) Experimental determination of order of reaction
(1) By measuring the rates of reaction at different reactant concentration
(2) By plotting graph of ln rate versus ln [X]
B. Examples of different reaction
1. First order reaction
a) Half life (t
½
)
b) Carbon-14 dating
c) Examples of calculation
2. Second order reaction
3. Zeroth order reaction
III. Collision theory and activation energy
A. Collision theory
1. Distribution of molecular speed (Maxwell-Boltzman distribution)
2. Effect of temperature change on molecular speeds
3. Collision theory and activation energy
a) Arrhenius equation
B. Determination of activation energy
1. By measuring the rate of reaction at different temperature
2. By plotting graph of ln k versus
1
T

3. By plotting graph of ln rate versus
1
T

Chemical Kinetics Page 2
IV. Energy profile of reaction
A. Transition state
1. Order of reaction leads to interpretation of reaction mechanism at molecular
level
a) Multi-stages reaction
(1) Alkaline hydrolysis of 2-chloro-2-methylpropane
(2) Reaction between bromide and bromate(V) in acidic medium
b) Rate determining step
2. Energetic stability and kinetic stability
B. Effect of catalyst
1. Characteristics of catalyst
2. Theory of catalyst
a) Homogeneous catalysis
b) Heterogeneous catalysis
3. Application of catalyst
a) Use of catalyst in Haber process and hydrogenation
b) Catalytic converter
c) Enzymes
V. Factors influencing the rate of reaction
A. Concentration
B. Temperature
C. Pressure
D. Surface area
E. Catalyst
F. Light
I. Rates of chemical reactions Page 1
Topic I. Rates of chemical reactions

Reference
Reading

5.1
A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 298–300
Assignment
Reading

Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 397–399, 401–403
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 352–354, 356–358

Syllabus
Definition of rate of reaction
Unit of rate of reaction
Measuring of rate of reaction

Notes
I. Rates of chemical reactions

A. Definition of rate of reaction

In every reaction, reactant is converted to product.

Reactant → Product

Rate of reactions is reflected by either rate of appearing of product or rate of disappearing of reactant.

Rate of reaction =
change in amount of product
time taken
= -
change in amount of reactant
time taken


The amount can be measured in term of mass, volume or any physical quantities related to amount.

If the reaction is performed in solution, the amount can also be expressed in term of concentration.

Rate of reaction =
∆ [product]
∆ t
= -
∆ [reactant]
∆ t
[ ] : concentration



Note : negative sign is added for the
∆ [reactant]
∆ t

because rate of reaction is always positive
but the quantity
∆ [reactant]
∆ t
is negative.


Rate of a reaction depends on : i. concentration
ii. temperature
iii. catalyst
iv. surface area
v. pressure
vi. light




1. Unit of rate of reaction

If the rate of reaction is expressed as the change in concentration of reactant or product with respect to time,
∆ [product]
∆ t
, the unit of rate of reaction would be conc
n
time
-1
(e.g.
mol dm
-3

s
, moldm
-3
s
-1
)


I. Rates of chemical reactions Page 2


B. Measuring the rate of reaction

By definition, rate is the change in certain quantity with respect to time. For example, speed is the change in
distance with respect to time.

Rate =
∆ amount
∆ time
Speed =
∆ distance
∆ time


1. Different approaches

There are two approaches to measure the rate, i. constant amount approach
ii. constant interval approach

a) Constant amount approach

Constant amount approach – Like Formula-1 car racing, a fixed no. of laps is set. The one who finishes all the
laps first would be the fastest one and would be the winner.


e.g. Rate of disproportionation of thiosulphate in acidic medium



Sodium thiosulphate and hydrochloric acid solution is put into a beaker. In acidic medium, thiosulphate
decomposes into yellow suspension of sulphur. Once the cross on the paper is masked by the yellow suspension,
the time is noted. As constant amount of sulphur precipitate is needed to mask the cross and the time taken is
noted, the rate of reaction can be estimated.

Rate of reaction =
Amount of sulphur precipitate formed
time taken


Rate ∝
1
time taken


Different concentration of thiosulphate and acid can be used to study the kinetic of the reaction.


I. Rates of chemical reactions Page 3


b) Constant interval approach

Constant interval approach – Like Daytona 24 hours car racing, a fixed interval e.g. 24 hours is set. The one who
can finish more laps in 24 hours would be the winner.

If the amount of a reactant or a product can be traced at constant intervals throughout the reaction, the rate of
reaction can also be determined.

For example, the reaction of disproportionation of thiosulphate, S
2
O
3
2-
(aq)
+ 2H
3
O
+
(aq)
→ SO
2(g)
+ S
(s)
+ 3H
2
O
(l)
, can
also be followed by titrating a fixed amount (e.g. 25.00 cm
3
) of reacting mixture at regular interval (e.g. 2 minutes)
with standard I
2(aq)
solution using starch indicator.

I
2(aq)
+ 2S
2
O
3
2-
(aq)
→ 2I
-
(aq)
+ S
4
O
6
2-
(aq)


Before titration, the disproportionation reaction must be quenched (stopped) first. This reaction is catalyzed by
acid, therefore, quenching can be done by neutralizing the acid with excess alkali, e.g. sodium hydrogencarbonate
(a weak alkali is preferred) or by sudden cooling of the reaction mixture.



Rate =
- d [S
2
O
3
2-
]
d t


The rate of reaction at any particular instant can be
calculated from the slope.

Rate = - slope

It is found that the reaction is first order with respect to
S
2
O
3
2-
(aq)
and zero order with respect to H
3
O
+
(aq)
.

Rate =
- d [S
2
O
3
2-
]
d t
= k [S
2
O
3
2-
]




In another example, for the catalytic decomposition of H
2
O
2(l)
in the presence of MnO
2(s)
catalyst, it can be
quenched by an acidic medium where acid is the negative catalyst to the reaction. The concentration of the H
2
O
2(l)

can be determined by titrating with standard MnO
4
-
(aq)
.

5H
2
O
2(aq)
+ 2MnO
4
-
(aq)
+ 6H
+
(aq)
→ 2Mn
2+
(aq)
+ 8H
2
O
(l)
+ 5O
2(g)


I. Rates of chemical reactions Page 4


2. Interpretation of physical measurements made in following a reaction

Besides titration, there are many other methods to follow a reaction. There are many quantities proportional to the
amount of a chemical in the reaction mixture. e.g. volume of gas, colour, conductivity and optical activity


a) Volume of gas formed

In the reaction between magnesium and hydrochloric acid, hydrogen gas is evolved.

Mg
(s)
+ 2HCl
(aq)
→ MgCl
2(aq)
+ H
2(g)


Rate = -
1
2

d[HCl
(aq)
]
dt
=
d[MgCl
2(s)
]
dt
=
d[H
2(g)
]
dt


The rate of reaction can be traced by monitoring the volume of the hydrogen gas evolved.

N.B. All pure solids have a constant density or concentration, equals
mass
volume
. Therefore, the rate of a reaction
is usually depending on the size of the solid particle rather than the amount of the solid present.





A graph of volume of hydrogen against time


b) Colorimetric measurement

If one of the reacting substances or products has a colour, the intensity of this colour will change during the
reaction. This method relies on the measurement of intensity of colour, therefore, it is called colorimetry. An
example will be the disappearance of the colour of bromine during the oxidation of methanoic acid by bromine:

Br
2(aq)
+ HCO
2
H
(aq)
→ 2Br
-
(aq)
+ 2H
+
(aq)
+ CO
2(g)


The change in colour intensity could be followed by a photoelectric device in a colorimeter, as shown in the
following figure.



Since the colour intensity is directly proportional to the concentration of Br
2(aq)
,

therefore, Rate ∝ -
d (colour intensity of the solution)
dt



Glossary
rate of reaction constant amount approach constant time approach initial rate of reaction
quenching colorimetry

I. Rates of chemical reactions Page 5

Past Paper
Question
93 1A 2 a iii
95 2A 2 b i
96 1B 4 d i ii iii
97 2A 3 a i ii iii
98 2A 3 a iii
99 1B 7 a

93 1A 2 a iii
2a Answer the following questions by choosing in each case one of the species listed below, putting it in the box and
giving the relevant equation(s).
Al
(s)
, AlCl
3(s)
, AlO
2
-
(aq)
, Na
(s)
, CO
3
2-
(aq)
, Cu
2+
(aq)
, P
4
O
10(s)
, S
(s)
, S
2
O
3
2-
(aq)
, Zn
2+
(aq)


iii Which species forms a pale yellow precipitate with dilute hydrochloric acid? 2
S
2
O
3
2-
(aq)
S
2
O
3
2-
(aq)
+ 2H
+
(aq)
→ S
(s)
+ SO
2(g)
+ H
2
O
(l)
2 marks
C Many candidates picked the wrong chemical species for the inorganic reactions in parts (i) to (iv).

95 2A 2 b i
2b In an aqueous solution, the decomposition of hydrogen peroxide in the presence of manganese(IV) oxide can be
represented by the following equation:
2H
2
O
2(aq)

MnO
2
 →  2H
2
O
(l)
+ O
2(g)


i For a given amount of manganese(IV) oxide, outline how you would use a chemical method to determine the
concentration of hydrogen peroxide, at different times, in the reaction mixture.
2
Withdraw a known volume of the reaction mixture ½ mark
and add to excess dilute H
2
SO
4
, ½ mark
titrate H
2
O
2
against standard MnO
4
-
. 1 mark
5H
2
O
2
+ 2MnO
4
-
+ 6H
+
→ 2Mn
2+
+ 8H
2
O + 5O
2


C This question was poorly answered. Candidates should brush up their skills in answering questions which involve
the description of experimental procedures.


96 1B 4 d i ii iii
4d In an experiment to determine the concentration of H
2
O
2
contained in a rainwater sample, 5.0 cm
3
of the sample
were mixed with an excess of a certain transition metal complex solution, giving a coloured mixture. The
absorbance of the mixture was measured by a colorimeter and was found to be 0.0273. When 5.0 cm
3
of 1.46 ×
10
-6
M H
2
O
2
(instead of the rainwater sample) were treated in the same way, an absorbance of 0.0398 was
recorded.

i Calculate the concentration of H
2
O
2
in the rainwater sample assuming that concentration is directly proportional to
absorbance.
2

conc
n
. of H
2
O
2
in the sample =
1.46 × 10
-6
0.0398
× 0.0273 1 mark
= 1.00 × 10
-6
M / 1.0 × 10
-6
M 1 mark
(Deduct ½ mark for answers given in 1 × 10
-6
M or 10
-6
M)

ii Why is the method of titration not suitable for the determination of the concentration of H
2
O
2
in the rainwater
sample ?
1
The concentration of H
2
O
2
in rainwater is too low to be determined by titrimetric method. 1 mark


iii Why is it not suitable to collect the rainwater sample for this experiment in an iron container ? 1
Fe can be oxidized by H
2
O
2
/ transition metal ions can catalyse the decomposition of H
2
O
2
. 1 mark

I. Rates of chemical reactions Page 6
97 2A 3 a i ii iii
3 The reaction of iodine with propanone in acidic solutions can be represented by the following equation
I
2(aq)
+ CH
3
COCH
3(aq)
→ CH
2
ICOCH
3(aq)
+ H
+
(aq)
+ I
-
(aq)


3a i The progress of the reaction can be monitored by a titrimetric method. Outline the experimental procedure. 6
ii State how the initial rate of the reaction can be determined from the titrimetric results.
iii Suggest another method to monitor the progress of the reaction.

98 2A 3 a iii
3a The table below lists the rate constants, k, at different temperatures, T, for the first order decomposition of a
dicarboxylic acid, CO(CH
2
CO
2
H)
2
, in aqueous solution :
CO(CH
2
CO
2
H)
2(aq)
→ CH
3
COCH
3(aq)
+ 2CO
2(g)

9
T / K 273 293 313 333 353
k / s
-1
2.46 × 10
-5
4.75 × 10
-4
5.76 × 10
-3
5.48 × 10
-2
?
iii Suggest a method to monitor the progress of the reaction.

99 1B 7 a
7a In a chemical kinetics experiment, samples of the reaction mixture are removed at regular time intervals for
titrimetric analysis.
Suggest TWO methods by which the reaction in the samples removed can be stopped or stowed down.


II. Order of reaction Page 1
Topic II. Order of reaction

Reference
Reading

5.2
Advanced Practical Chemistry, John Murray (Publisher) Ltd., 96–99, 103–106
A-Level Chemistry Syllabus for Secondary School (1995), Curriculum Development Council, 197–198
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 403–410
Experiment – Determination of the order of reaction of disproportionation of thiosulphate in acidic medium

Assignment
Reading

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 302–308
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 358–365

Syllabus
Order of reaction
Rate Law

Notes
II. Order of reaction

A. Rate Law or rate equation

Rate Law or rate equation – A mathematical expression relates the concentration of a species with the rate
of reaction or time.

There are three different forms of rate law i. ordinary form
ii. differential form
iii. integrated form
Examples of rate law (ordinary form)

e.g. H
2(g)
+ Br
2(g)
→ 2HBr
(g)
Rate =
k’[H
2
][Br
2
]
½
1+k’’(
[HBr]
[Br
2
]
)


e.g. 2NO
(g)
+ O
2(g)
→ 2NO
2(g)
Rate = k[NO]
2
[O
2
]

e.g. 2H
2(g)
+ 2NO
(g)
→ 2H
2
O
(g)
+ N
2(g)
Rate = k[NO]
2
[H
2
]


N.B. The rate equation has no direct relationship with the stochiometric coefficient. It can only be
determined by experiment.

According to collision theory, the rate of reaction always increases with concentration of reactant.

concentration of reactant ↑ ⇒ rate of reaction ↑

In some reactions, the rate is directly proportional to the concentration. i.e. double the concentration of a reactant,
only double the rate of reaction. But in some reactions, double the concentration of a reactant may cause 4 folds
increase in reaction rate. The relationship needs not be linear.

e.g. H
2(g)
+ I
2(g)
→ 2HI
(g)


For the above reaction, it is found experimentally that

Rate ∝ [H
2
] The reaction is first order with respect to H
2(g)


Rate ∝ [I
2
] The reaction is first order with respect to I
2(g)


Rate ∝ [H
2
][I
2
]

Rate = k [H
2
][I
2
] Rate law or rate equation (an overall second order reaction)

k, the proportionality constant, is known as rate constant which depends on temperature only.
II. Order of reaction Page 2


Rate has the unit (mole dm
-3
s
-1
) and concentration has the unit (mole dm
-3
). Therefore, the unit of rate constant, k,
depends on actually what the rate equation is.

e.g.
In the rate equation, Rate = k [H
2
][I
2
], k =
Rate
[H
2
][I
2
]

unit of k =
mole dm
-3
s
-1
mole dm
-3
· mole dm
-3 = mole
-1
dm
3
s
-1


e.g.
For the reaction, 2H
2(g)
+ 2NO
(g)
→ 2H
2
O
(g)
+ N
2(g)
, Rate = k[NO]
2
[H
2
], k =
Rate
[NO]
2
[H
2
]

unit of k =
mole dm
-3
s
-1
(mole dm
-3
)
2
· mole dm
-3 = mole
-2
dm
6
s
-1





1. Differential form and Integrated form of rate law
(The derivation of the integrated form of rate law is not required in A-Level)

Rate of reaction =
∆ [product]
∆ t
= -
∆ [reactant]
∆ t


By using notation of calculus

Rate of reaction =
d [product]
dt
=
- d [reactant]
dt
(differential form of rate law)

For the reaction, H
2(g)
+ I
2(g)
→ 2HI
(g)


Rate =
- d [H
2
]
dt
=
- d [I
2
]
dt
=
1
2

d [HI]
dt
and Rate = k[H
2
][I
2
]

∴ Rate =
- d [H
2
]
dt
= k[H
2
][I
2
] Keep the [I
2
] constant by using excess I
2


- d [H
2
]
dt
= k’[H
2
] where k’ = k [I
2
], the reaction is first order with respect to H
2(g)


-
d[H
2
]
[H
2
]
= k’dt




[H
2
]
0
[H
2
]
-
d[H
2
]
[H
2
]
= k'


0
f
dt
[H
2
] is the concentration at time = t
[H
2
]
0
is the concentration at time = 0


- [ ln [H
2
] ]
[H
2
]
[H
2
]
0
= k' t

- (ln [H
2
] - ln [H
2
]
0
) = k’t

ln
[H
2
]
0
[H
2
]
= k’t or
[H
2
]
0
[H
2
]
= e
k't
(Integrated form of rate law)

at t = 0 [H
2
]
0
= [H
2
]

at t = ∞
[H
2
]
0
[H
2
]
= ∞ ⇒ [H
2
] = 0
II. Order of reaction Page 3


2. Graphical presentation of reaction rate

For the reaction H
2
O
2(aq)
+ 2I
-
(aq)
+ 2H
+
(aq)
→ 2H
2
O
(l)
+ I
2(aq)


The completeness of the reaction can be monitored by following the concentration of one of the reactant or
product.



Rate of reaction =
∆ [product]
∆ t
= -
∆ [reactant]
∆ t


Using notation of calculus

Rate =
d [I
2
]
dt
=
- d [H
2
O
2
]
dt
=
1
2

- d [I
-
]
dt
=
1
2

- d [H
+
]
dt


Note the rate of disappearing of I
-
(aq)
is twice of the rate
of disappearing of H
2
O
2(aq)
.

Although H
2
O
(l)
is one of the product, it is also the
solvent. Because it is in large excess, its concentration
would be rather constant.




For the reaction of decomposition of NO
2(g)
at 300 ºC

2NO
2(g)
→ 2NO + O
2(g)


Rate =
1
2

- d [NO
2
]
dt
=
1
2

d [NO]
dt
=
d [O
2
]
dt



Notation of calculus is preferable to
∆ [product]
∆ t

or -
∆ [reactant]
∆ t
since the former one reflects the rate
of reaction at a particular instant instead of average rate
over a period of time.


II. Order of reaction Page 4


3. Order of reaction

Order of individual reactant – The order of a reaction with respect to a given reactant is the power of that
reactant’s concentration in the experimentally determined rate equation.

Overall order of reaction – The (overall) order of the reaction is the sum of the powers of the concentration
terms in the experimentally determined rate equation.

e.g. 2H
2(g)
+ 2NO
(g)
→ 2H
2
O
(g)
+ N
2(g)


Rate = k[NO]
2
[H
2
] The reaction is second order with respect to NO
(g)

The reaction is first order with respect to H
2(g)

The overall order of the reaction is 3 or the reaction is a third order reaction.



A zeroth order means that the rate of reaction is
independent of the concentration of that reactant.

A first order means that the rate of reaction is directly
proportional to the concentration of that reactant.

A second order means that the rate of reaction is
directly proportional to the square of the concentration
of that reactant.

In general, the higher the order of a reactant, the more
dependent will be the rate of reaction on the
concentration of that reactant.


II. Order of reaction Page 5


a) Experimental determination of order of reaction

(1) By measuring the rates of reaction at different reactant concentrations

Suppose a reaction X + Y → Z has the rate law rate = k[X]
a
[Y]
b


The order of reaction with respect to X (i.e. a) can be determined by measuring the rate of reaction with different
concentration of X, while the concentration of Y is kept constant.

rate
1
= k[X]
1
a
[Y]
b
(1)
rate
2
= k[X]
2
a
[Y]
b
(2)

(1) ÷ (2)
rate
1
rate
2
=
k[X]
1
a
[Y]
b
k[X]
2
a
[Y]
b = (
[X]
1
[X]
2
)
a


ln
rate
1
rate
2
= a ln (
[X]
1
[X]
2
)

a = ln
rate
1
rate
2
÷ ln (
[X]
1
[X]
2
)

(2) By plotting graph of ln rate versus ln [X[

The order of reaction with respect to X can also be determined by graphical method. Since more than 2 readings
are used to determine the order, the order determined will be more accurately than the above method.

For the same reaction X + Y → Z

rate = k[X]
a
[Y]
b


rate = k'[X]
a
Keep [Y] constant by using excess Y, since b is also a constant. [Y]
b
will be a constant.

ln rate = ln (k'[X]
a
)

ln rate = ln k' + a ln [X]

According to the above equation, the order of a reaction (i.e. a) with respect to a reactant (i.e. X) can be
determination by measuring the rates of reaction (i.e. rate) with different concentrations of the reactant (i.e. [X[).

The order of reaction can be obtained from the slope of the graph with (ln rate) plotting against ln [X].



II. Order of reaction Page 6


B. Examples of different reaction

1. First order reaction

First order reaction – the rate of reaction is directly proportional to the concentration of the reactant.

Since the rate of decay is directly proportional to the amount of isotope remains. This form an exponential decay
curve.


After 5 half-lives, the fraction remaining will be
= ½ × ½ × ½ × ½ × ½
= 0.03125

= 3.125%

Radioactive decay is said to be a first order reaction,
since the rate is proportional to the number of
radioactive isotopes present.



a) Half life (t
½
)

The rate of radioactive decay reaction is directly proportional to the abundance of the radioactive isotope.
Radioactive decay is so special that the rate of reaction is even independent of temperature. This is the only
reaction which is independent of temperature.

Radiation ∝ No. of isotope ∝ Rate of decay

Rate of decay ∝ I I : abundance of radioactive isotope ∝ no. of isotope
Rate = k I =
-d I
dt


By integration according to time.

ln
I
0
I
= kt or
I
0
I
= e
kt
I
0
: abundance of radioactive isotope at time = 0
I : abundance of radioactive isotope at time = t

By definition, half life (t
½
), is the time taken by a given amount of radioactive isotope to decay to half of
the original amount.

ln
I
0
I
= kt when t = t
½
then I
0
= 2 I

ln
2I
I
= kt
½
= ln 2 t
½
=
ln 2
k
=
0.693
k


N.B.: It can be seen that the half life (t
½
) of a first order reaction is related to the decay constant (k).
II. Order of reaction Page 7


b) Carbon-14 dating

In nature the,
7
14
N in the air, is transmutated to
6
14
C by the neutron from the cosmic ray.

i.e.
7
14
0
1
N n + ÷ → ÷ + 6
14
1
1
C H

6
14
C isotope is radioactive. At the same time, it undergoes beta decay which is a first order reaction.

6
14
7
14
1
0
C N e ÷ → ÷ +



As a result of this simultaneous formation and decay of
6
14
C , the atmosphere contains a constant concentration of
6
14
C . The
6
14
C is present as
6
14
2
CO . This
6
14
2
CO enters plants via photosynthesis and animals via the food chain.
Therefore, all living things have a constant proportion of their carbon in form of
6
14
C . However, when the animal
or plant dies, replacement of
6
14
C ceases while decay of
6
14
C continues.

It is assumed that the concentration of
6
14
2
CO in atmosphere remains unchanged throughout million of years. By
comparing the content of
6
14
C in archaeological specimens with that in similar living materials living at the present
time, it is possible to estimate the age of the specimens.

c) Example of calculation

Half life (t
½
) of
6
14
C = 5730 years

If 32 counts per minute per gram of carbon is emitted by living organisms, while a fossilized bone gives 8 counts
per minute per gram of carbon, calculate the age of the fossil.

The number of counts is proportional to the abundance of the radioactive isotope.

ln
I
0
I
= kt and t
½
=
ln 2
k
=
0.693
k


ln
32
8
=
ln 2
t
½
· t

ln 4 =
ln 2
5730
· t

t =
ln 4 · 5730
ln 2
= 2 × 5730 = 11460 years

II. Order of reaction Page 8


2. Second order reaction

Second order reaction – the rate of reaction is directly proportional to the square of the concentration of
the reactant.

Consider the reaction A
(l)
+ B
(l)
→ C
(l)
+ D
(l)
which is first order with respect to A, but second order with respect to
B.

Rate = k[A][B]
2


if we keep A in large excess, then [A] will remain a constant throughout the reaction.

Rate = k’[B]
2


the reaction becomes second order with respect to B, where k’ = k [A]

Rate = k’[B]
2
=
- d[B]
dt


- k’dt =
d[B]
[B]
2



0
t
- k' dt =


[B]
0
[B]
d[B]
[B]
2

- k' t =

-
1
[B]
[B]


[B]
0
- k' t =
\
|
.
|
-
1
[B]
-
\
|
.
|
-
1
[B]
0
- k' t =
1
[B]
0
-
1
[B]


1
[B]
= k' t +
1
[B]
0


By plotting a graph
1
[B]
versus t, the slope will equal to k’. Since k’ = k [A], the rate constant (k) can be
determined.

Half life (t
½
) of second order reaction

1
[B]
= k' t +
1
[B]
0
at t = t½, [B] =
1
2
[B]
0


1
½[B]
0
= k' t
½
+
1
[B]
0


k' t
½
=
1
½[B]
0
-
1
[B]
0


k' t
½
=
2
[B]
0
-
1
[B]
0
=
1
[B]
0

t
½
=
1
k
'
[B]
0


N.B. In contrast to the constant half life of a first order reaction, half life of a second order reaction is
depending on the initial concentration of the reactant.
II. Order of reaction Page 9


3. Zeroth order reaction

Zeroth order reaction – the rate of reaction is independent of the concentration of the reactant.

Actually, there is no reaction with an overall order equals zero. But zero order reaction with respect to individual
reactant is commonly found in catalytic reaction.

In synthesis of ammonia by Haber process, N
2(g)
+ 3H
2(g)
d 2NH
3(g)
, it is found that the reaction is zero order
with respect to both N
2(g)
and H
2(g)
.

This is because Fe catalyst is used in the synthesis. The availability of the surface of Fe is the limiting factor of the
reaction. Both N
2(g)
and H
2(g)
are in large excess comparing with Fe catalyst.


For a general zero order reaction, A → product

Rate = k[A]
0
= k(1) = k

Rate = k =
- d[A]
dt


- kdt = d[A]



0
t
-k dt =


[A]
0
[A]
d[A]

-kt = [ ] [A]
[A]

[A]
0


- kt = [A] - [A]
0


[A] = - kt + [A]
0


Half life of zero order reaction

[A] = - kt + [A]
0


1
2
[A]
0
= - kt
½
+ [A]
0


kt
½
= [A]
0
-
1
2
[A]
0
=
1
2
[A]
0


t
½
=
[A]
0
2 k


Glossary
order of reaction rate law / rate equation rate constant differential form of rate law
integrated form of rate law overall order of reaction half-life carbon-14 dating
decay constant

II. Order of reaction Page 10

Past Paper
Question
90 1A 2 d i
91 2A 1 a iii
92 1A 2 a i ii 92 2A 2 a ii iii
93 2A 2 b i ii
94 1B 4 e i ii iii
95 1A 1 d i ii 95 2A 2 a ii 95 2A 2 b ii
96 1A 1 b i ii 96 2A 3 c i ii
97 2A 3 b i ii c
98 2A 2 b i ii 98 2A 3 a ii
99 2A 3 a i ii

90 1A 2 d i
2d Consider the reaction A
(l)
+ B
(l)
→ C
(l)
+ D
(l)
which is first order with respect to A, but second order with respect to
B.

i Give a rate expression for this reaction 1
Rate = k[A][B]
2
1 mark

91 2A 1 a iii
1a
The radioactive decay of
92
238
U may be represented by
92
238
U →
82
206
Pb + α + β.

iii
The age of a mineral containing
92
238
U and
82
206
Pb can be estimated from the mole ratio,
82
206
Pb :
92
238
U . It is assumed
that all
82
206
Pb has arisen only by the decay of the uranium and that all the subsequent decays are small in
comparison with that of
92
238
U which has a half-life of 4.51 × 10
9
years. Calculate the age of the mineral if the
mole ratio of
82
206
Pb :
92
238
U is 0.231 : 1.000.
Note : The integrated form of a first order reaction my be expressed as ln
I
I
kt
0
= where I
0
is the initial
concentration and I is the concentration at time t.
4
The decay constant k can be calculated from the half-life.
k =
ln
2
1
4.51 10
9
×
= 1.5369 × 10
-10
year
-1
1½ mark
The ratio of Pb : U = 0.231 : 1.000
The amount of U at the beginning (I
0
) = 1.000 + 0.231 = 1.231 ½ mark
The amount of U at time t (I) = 1 ½ mark
∴ t =
ln .
.
1231
15369 10
10
×

= 1.35 × 10
9
years (no / wrong unit -½) (3 to 4 sig. fig. if not -½) 1½ mark

C Many candidates were not able to establish the correct ratio of I
0
/I, and hence failed to obtain the correct answer.

92 1A 2 a i ii
2a
For the first order reaction, A product
k
÷ → ÷ , the integrated form of the rate equation is [A] [A]
e
0
kt
=

, where
[A] and [A]
0
are the concentrations of A at time = t and time = 0 respectively.

i
Starting from this equation, derive the relationship between the half-life t
½
of the reaction and the rate constant k.
1
The half life of the reaction is defined by the concentration condition, [A] = [A]
0
/2. ½ mark
Substituting into the integrated rate law give [A]
0
/2 = [A]
0
e
-kt
.
This is followed by taking the natural logarithm to give ln(0.5) = -kt
½
. ½ mark
Therefore, t
½
= 0.693/k.

ii Without using the half-life method, show how you would determine the rate constant k from a set of experimental
measurements of concentration at various times.
2
From the integrated rate equation, an experimental straight line plot can be obtained by taking the ln of the
integrated rate equation, ln[A] = ln[A]
0
- kt. ½ mark
Which can be rearranged to give an equation in the form of a straight line (y = mx +b)
ln [A] = -kt + ln[A]
0
1 mark
Therefore, k can be determined from the slope of the plot ln[A] vs t. ½ mark

C A good example to demonstrate that most candidates lack the most basic mathematical application / manipulation
skills. No knowledge of calculus was required in answering this question. The candidates should have the ability
to take In and to recognize equations in the form of a straight line. Few candidates were able to score full marks in
this question.


II. Order of reaction Page 11
92 2A 2 a ii iii
2a In acid solution, chlorate(V) ions, ClO
3-
, slowly oxidize chloride ions to chlorine. The following kinetic data are
obtained at 25°C.
[ClO
3
-
]/mol dm
-3
[Cl
-
]/mol dm
-3
[H
+
]/mol dm
-3
Initial rate/mol dm
-3

0.08 0.15 0.20 1.0 × 10
-5

0.08 0.15 0.40 4.0 × 10
-5

0.16 0.15 0.40 8.0 × 10
-5

0.08 0.30 0.20 2.0 × 10
-5


ii Determine the order of the reaction with respect to each reactant. 3
Since the rate of reaction
Rate = k[ClO
3
-
]
l
[Cl
-
]
m
[H
+
]
n
1 mark
10 10
4 0 10
0 08 015 0 2
0 08 015 0 4
1
4
2
4
4
1
2
2
5
5
.
.
( . ) ( . ) ( . )
( . ) ( . ) ( . )
log log
×
×
= ⇒ =
|
\

|
.
|
⇒ − = ⇒ =


l m n
l m n
n
n n
Similarly l = 1 and m = 1. with working max. 3 marks
without working: all correct 2 marks or wrong 0 mark

iii Determine the rate constant at this temperature. 2
Rate = k[ClO
3
-
][Cl
-
][H
+
]
2
1 mark
k
rate mol dm s
mol dm
mol dm s = =
×
= ×
− − −

− − −
[ClO ][Cl ][H ]
3
- - + 2
10 10
0 08 015 0 2
2 08 10
5
2
3 1
3 4
2 3 9 1
.
( . )( . )( . ) ( )
. 1 mark
no unit -½ mark

C Many candidates gave wrong units for the rate constant.

93 2A 2 b i ii
2b Given the following data for the reaction at 298 K
2C + 3D + E → P + 2Q
Experiment [C] / mol dm
-3
[D] / mol dm
-3
[E] / mol dm
-3
initial rate / mol dm
-3
s
-1
1 0.10 0.10 0.10 3.0 ? 10
-3
2 0.20 0.10 0.10 2.4 ? 10
-2
3 0.10 0.20 0.10 3.0 ? 10
-3
4 0.10 0.10 0.30 2.7 ? 10
-2


i Deduce the rate law of the above reaction. 4
Rate = k[C]
x
[D]
y
[E]
z

Since
rate 1
rate 2
= (
0.10
0.20
)
x
=
3.0 × 10
-3
2.4 × 10
-2
=
1
8
∴ x = 3 1 mark

rate 1
rate 3
= (
0.10
0.20
)
y
=
3.0 × 10
-3
3.0 × 10
-3
= 1 ∴ y = 0 1 mark

rate 1
rate 4
= (
0.10
0.30
)
z
=
3.0 × 10
-3
2.7 × 10
-2
=
1
9
∴ z = 2 1 mark
Rate = k[C]
3
[D]
0
[E]
2
= k[C]
3
[E]
2
1 mark

ii Calculate the rate constant. 2
Using results of experiment 1
3.0 × 10
-3
= k (0.10)
3
(0.10)
2

k = 300 (mol dm
-3
)
-4
s
-1
(1 mark for answer, 1 mark for correct unit) 2 marks

C Some candidates could not do the calculation of the rate constant, due to their unfamiliarity in handling
exponential values.


II. Order of reaction Page 12
94 1B 4 e i ii iii
4e In an experiment to determine the rate constant at 298 K for the decomposition of sodium thiosulphate by a large
excess of dilute hydrochloric acid, the time, t, taken for a certain amount of sulphur to appear was measured.
Under these conditions: Rate = k’[S
2
O
3
2-
].

i Write a balanced equation for the reaction between hydrochloric acid and sodium thiosulphate. 1
S
2
O
3
2-
(aq)
+ 2H
+
(aq)
→ H
2
O
(l)
+ SO
2(g)
+ S
(s)

or Na
2
S
2
O
3
+ 2HCl → 2NaCl + S + SO
2
+ H
2
O 1 mark

ii Describe how you would carry out this experiment, indicating the measurements you would take. 4
Make standard [S
2
O
3
2-
] solution of different molarity and place equal volume of these solutions in conical flasks.
1½ mark
Measure temperature of solution / set thermostat to 298 K ½ mark
Add a fixed volume of acid to Na
2
S
2
O
3
(using measuring cylinder) ½ mark
Start stop clock ½ mark
Note time, t, when a black “X” marked on a cardboard becomes invisible when looking through the flask. 1 mark

iii What quantities would you plot on a graph for the determination of the rate constant k’ at 298 K? 1
1
t
/ s
-1
and [S
2
O
3
2-
(aq)
] / mol dm
-3
1 or 0 mark

C Many candidates have previous experience of this experiment, but nonetheless their answers were poor. The
temperature control was omitted in most cases, and many candidates did not give a method for measuring the time
taken for the formation of a certain amount of sulphur. Some utilized titration, while others used a colorimeter or
filtering and weighing to quantitate sulphur, but none of these answers were acceptable. In (iii), candidates did not
know that rate is inversely proportional to reaction time.


95 1A 1 d i ii
1d The iodination of propanone is catalysed by hydrogen ions. The overall equation is:
CH
3
COCH
3(aq)
+ I
2(aq)
→ CH
3
COCH
2
I
(aq)
+ HI
(aq)

Using four mixture B, C, D and E, the progress of the reaction was followed by colorimetric measurement. The
results are tabulated below.

Composition by volume
of mixture /cm
3


Mixture propane water 1.00 M HCl 0.05 M I
2
in KI Initial rate / mol dm
-3
s
-1

B 10.0 60.0 10.0 20.0 4.96 × 10
-6

C 10.0 50.0 10.0 30.0 5.04 × 10
-6

D 5.0 65.0 10.0 20.0 2.45 × 10
-6

E 10.0 65.0 5.0 20.0 2.47 × 10
-6

i Determine the effects of the changes in concentration of each of the reactants (iodine and propanone) and the
catalyst (hydrochloric acid) on the reaction rate. Write the rate expression for the reaction.
2
I
2
, use B and C : rate independent of [I
2
] ½ mark
propane, use B and D : rate ∝ [propanone] ½ mark
H
+
, use B and E : rate ∝ [H
+
] ½ mark
rate = k [H
+
] [CH
3
COCH
3
] ½ mark

ii For mixture B, calculate the rate constant for the reaction at the temperature of the experiment.
(Density of CH
3
COCH
3
= 0.789 gcm
-3
)
2

rate = 4.96 × 10
-6
= k [0.1] [
100 × 0.789
58.078
] 1 mark
k =
58.078 × 4.96 × 10
-6
0.1 × 100 × 0.789
= 3.65 × 10
-5
mol
-1
dm
3
s
-1
1 mark
(½ mark for numerical answer; ½ mark for unit)

C Many candidates were unable to deduce the quantitative relation between reaction rate and change in
concentration of the reactants, merely stating that 'rate increases with increased concentration'. In some cases, the
experimental nature of the rate results was not appreciated, so that the order with respect to iodine was calculated
to be non-zero or fractional. Some candidates had difficulty in calculating the concentrations of the reactants from
the data given.


II. Order of reaction Page 13
95 2A 2 a ii
2a
88
228
Ra decays by the emission of β particles. The half-life for the decay is 6.67 years.

ii
A sample containing 0.50 g of
88
228
Ra is kept in a closed container. Calculate the mass of
88
228
Ra remaining after 5
years.
(The decay of a radioisotope can be described by the equation, N
t
= N
0
e
-kt
, where N
0
and N
t
respectively
represent the initial number and number at time t of the radioisotope, and k is the decay constant.)
3

k =
ln 2

= 0.104 year
-1
1 mark
ln
0.5
N
t
= 0.104 (5) 1 mark
N
t
= 0.297 g 1 mark


95 2A 2 b i ii
2b In an aqueous solution, the decomposition of hydrogen peroxide in the presence of manganese(IV) oxide can be
represented by the following equation:
2H
2
O
2(aq)

MnO
2
÷ → ÷÷ 2H
2
O
(l)
+ O
2(g)


i For a given amount of manganese(IV) oxide, outline how you would use a chemical method to determine the
concentration of hydrogen peroxide, at different times, in the reaction mixture.
2
Withdraw a known volume of the reaction mixture ½ mark
and add to excess dilute H
2
SO
4
, ½ mark
titrate H
2
O
2
against standard MnO
4
-
. 1 mark
5H
2
O
2
+ 2MnO
4
-
+ 6H
+
→ 2Mn
2+
+ 8H
2
O + 5O
2


ii How would you use the results obtained in (i) to show graphically that the decomposition is first order with
respect to H
2
O
2
and to find the rate constant of the decomposition ?
4
Plot [H
2
O
2
] against t to obtain the following graph
2 marks
for first order reaction t
½
= constant and k =
ln 2
t
½
2 marks
OR
Plot ln [H
2
O
2
] against t to obtain a straight line 1 mark
ln
[H
2
O
2
]
[H
2
O
2
]
0
= - kt ⇒ ln[H
2
O
2
] - ln[H
2
O
2
]
0
= -kt 2 marks
for first order reaction, slope = -k. 1 mark

C This question was poorly answered. Candidates should brush up their skills in answering questions which involve
the description of experimental procedures.


96 1A 1 b i ii
1b Carbon-14,
14
C, is radioactive, emitting β-particles.
i Write an equation for the decay of
14
C. 1

6
14
1
0
7
14
C e N → +

or
6
14
7
14
C N → + β 1 mark

ii A charcoal sample from the ruins of an ancient settlement was found to have a
14
C/
12
C ratio 0.60 times that found
in living organisms.
(1) Explain why the
14
C/
12
C ratio in the charcoal sample is smaller than that in living organisms.
(2) Given that the half-life for the decay of
14
C is 5730 years, calculate the age of the charcoal sample.
(Note : The integrated form of the rate expression for radioactive decay can be represented by the following
3
II. Order of reaction Page 14
equation :
log
10
(
N
0
N
t
) =
0.301
t
½
t
where N
0
is the initial number of radioactive nuclei;
N
t
is the number of radioactive nuclei at time t;
t
½
is the half-life for the decay)
(1) In the piece of charcoal intake of C stops; ½ mark
decay of
14
C continues while
12
C remains constant ∴
14
C /
12
C ratio drops ½ mark
(2) log
1.0
0.6
=
0.301 t
5730
⇒ t = 4223 ± 3 year 1 mark + 1 mark
(Deduct ½ marks for wrong /no unit)


96 2A 3 c i ii
3c The following equation represents the decomposition of N
2
O
5(g)
:
2N
2
O
5(g)
→ 4NO
2(g)
+ O
2(g)

The progress of the above decomposition can be followed by measuring the partial pressures of N
2
O
5(g)
, P
N O
2 5
, at
different times, t. The table below lists the results of such an experiment :

t / minute 0 100 200 300 400 550 800 1250
P
N O
2 5
/ kPa 13.3 10.9 8.9 7.2 5.9 4.4 2.7 1.1

i By plotting a suitable graph, find the order of the decomposition. 3
t 0 100 200 300 400 550 800 1250
ln(P
N
2
O
5
) 2.59 2.39 2.19 1.97 1.77 1.48 0.99 0.10
or log(P
N
2
O
5
) 1.12 1.04 0.95 0.86 0.77 0.4 0.43 0.04

Plotting the following graph 2 marks

(1 mark for the straight line, 1 mark for correct labelling of the axes)
the reaction is 1st order 1 mark

ii Using your graph in (i), determine the rate constant of the decomposition. 2
From the plot of ln(P
N
2
O
5
) against t,
- slope = k 1 mark
= 1.99 × 10
-3
minute
-1
(2.2 × 10
-3
– 1.8 × 10
-3
min
-1
) 1 mark
(1 mark for numerical answer, ½ mark for unit)


II. Order of reaction Page 15
97 2A 3 b i ii c
3 The reaction of iodine with propanone in acidic solutions can be represented by the following equation
I
2(aq)
+ CH
3
COCH
3(aq)
→ CH
2
ICOCH
3(aq)
+ H
+
(aq)
+ I
-
(aq)


3b The following initial rates and initial concentrations were obtained in an experiment at 298 K: 5
Initial concentration / mol dm
-3

Initial rate / mol dm
-3
s
-1
[I
2(aq)
] [CH
3
COCH
3(aq)
] [H
+
(aq)
]
3.5 × 10
-5
2.5 × 10
-4
2.0 × 10
-1
5.0 × 10
-3

3.5 × 10
-5
1.5 × 10
-4
2.0 × 10
-1
5.0 × 10
-3

1.4 × 10
-4
2.5 × 10
-4
4.0 × 10
-1
1.0 × 10
-2

7.0 × 10
-5
2.5 × 10
-4
4.0 × 10
-1
5.0 × 10
-3

i Deduce the rate equation for the reaction.
ii Calculate the rate constant for the reaction at 298 K.
3c Suppose that the reaction takes place in a buffer solution of pH 4. On the basis of your results in (b) deduce the
half-life of the reaction at 298 K.
4

98 2A 2 b i ii
2b Potassium-40 is radioactive and decays to give the stable isotope, argon-40. The half-life of the decay is 1.27 ×
10
9
years.
5
i In a rock sample, the ratio of
40
K to
40
Ar is 1 to 9. Estimate the age of the rock sample.
ii The above method of estimation is based on several assumptions. One of the assumptions is that all
40
Ar present in
the rock sample is derived from the decay of
40
K. Give one other assumption relating to
40
Ar.


98 2A 3 a ii
3a The table below lists the rate constants, k, at different temperatures, T, for the first order decomposition of a
dicarboxylic acid, CO(CH
2
CO
2
H)
2
, in aqueous solution :
CO(CH
2
CO
2
H)
2(aq)
→ CH
3
COCH
3(aq)
+ 2CO
2(g)

9
T / K 273 293 313 333 353
k / s
-1
2.46 × 10
-5
4.75 × 10
-4
5.76 × 10
-3
5.48 × 10
-2
?
ii Estimate the rate constant of the reaction at 353 K and hence calculate the half-life of the reaction at the same
temperature.


99 2A 3 a i ii
3a Consider the following data for the reaction
A + B → products

Initial concentration / mol dm
-3

[A] [B] Initial rate / mol dm
-3
s
-1

4.0 × 10
-2
4.0 × 10
-2
6.4 × 10
-5

8.0 × 10
-2
4.0 × 10
-2
12.8 × 10
-5

4.0 × 10
-2
8.0 × 10
-2
6.4 × 10
-5


For this reaction,
i deduce its rate equation,
ii calculate the rate constant, and

III. Collision theory and activation energy Unit 1 Page 1
Topic III. Collision theory and activation energy Unit 1

Reference
Reading

5.3


Assignment
Reading

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 172–173, 310–311
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 410–412
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 140–142, 266–367, 369

Syllabus
Distribution of molecular speed
Effect of temperature change on molecular speeds
Collision theory and activation energy
Arrhenius equation

Notes
III. Collision theory and activation energy

A. Collision theory

1. Distribution of molecular speed (Maxwell-Boltzmann distribution)


For a sample of gas at a specific temp, it is found that most particles possess
speeds about average speed. Only very few have very high or very low speed
(extreme speeds).

This gives a Maxwell-Boltzmann distribution. Maxwell-Boltzmann
distribution is different from normal distribution in the way that it is not
symmetrical.

Origin of Maxwell-Boltzmann distribution

Gas particles are in constant random motion. During collisions, some
particles gain energy from the others and some particles loss energy to the
others.
After a series of collisions, different particles will have different speed.


Maxwell-Boltzmann
distribution


2. Effect of temperature change on molecular speeds


As temperature increases, collisions among the particles
become more vigorous. This causes a wider spread in
particle speed.

The kinetic energy of the gas increases with increasing
temperature, so the peak of most probable speed shifts
to the right.

The area under the curve represents the total no. of
particle and should remain constant and independent of
the temperature. This makes the height of the peak
drops at higher temperature.




III. Collision theory and activation energy Unit 1 Page 2


3. Collision theory and activation energy

To simplify the discussion, a sample of ideal gas is considered first.

Except in self decomposition, all reacting particles must get in contact with other for reaction to take place.

The collision frequency (Z) is proportional to the velocity of the particle (c).

Z ∝ c

Conclusion 1 – Reaction takes place as a result of collision.


The simple collision theory is contradictory to the experimental finding. For most reactions, every 10 K increase in
temperature will double the reaction rate. Meanwhile, an increase in 10 K at room temperature will only cause 1.6
% increase in particles velocity.

Reaction is something more than just collision.

Experimental finding finds that reaction rate increases exponentially with increasing temperature.



Refering to the Maxwell-Boltzmann distribution of
molecular speed, by mathematical approximation, the
fraction of the shaded area is represented by e
E
RT
A

, where
E
A
is called the activation energy.


shaded area
total area

=
no. of particles having energy greater than E
A
total no. of particles

= e
E
RT
A



The value
e
E
RT
A

increases exponentially with
temperature.


In order to explain the expontential increase of reaction rate with temperature, it is assumed that a reaction will
only take place if the collision has an energy exceeds the activation energy E
A
. Different reaction has different
value of E
A
.


Rate ∝ Z
and Rate ∝ e
E
RT
A


therefore Rate ∝ Ze
E
RT
A


Z : collision frequency
R : (universal) gas constant = 8.314 JK
-1
mol
-1

E
A
: activation energy
T : temperature in Kelvin


Conclusion 2 – Reaction only occurs when the collision exceeds certain threshold energy, activation energy.

III. Collision theory and activation energy Unit 1 Page 3


Since the rate of reaction is directly proportionally to the rate constant, k.


Rate ∝ k

k ∝ Ze
E
RT
A

Z : collision frequency

k = PZe
E
RT
A

P : steric factor / orientation factor (a proportionality constant)

k = Ae
E
RT
A

where A = PZ A is called Arrhenius factor


Through experiment, P is found to be a factor always smaller than 1. It is a factor reflects the steric factor and the
fraction of collisions with effective orientation.



Conclusion 3 – Reaction only occurs when the colliding particles are correctly oriented to one another.

According to collision theory, a reaction will take place only if the following 3 conditions are satisfied and the
collision is then called an effective collision.

i. Collision
ii. Exceed activation energy
iii. Correct orientation of collision


a) Arrhenius equation


The equation k = Ae
E
RT
A

is called Arrhenius equation.

This equation relates the temperature and activation
energy with rate constant, thus rate of reaction.
k : rate constant (a constant depends on
temperature only)
A : Arrhenius constant
E
A
: activation energy
e
E
RT
A

: activation state factor (fraction of particle has
energy greater than E
A
at temperature T)


Rate of reaction = k [Reactants]
n
= Ae
E
RT
A

[Reactants]
n


From the above equation, it can be seen that the rate of a reaction is depending on
1. Temperature
2. Nature of the reaction (Activation energy, i.e. Steric factor & Orientation factor)
3. Concentration of reactants


Glossary
Maxwell-Boltzmann distribution collision theory activation energy collision frequency (Z)
Gas constant (R) threshold Arrhenius constant (factor)

III. Collision theory and activation energy Unit 1 Page 4

Past Paper
Question
96 2A 1 b i ii
98 2A 3 b i ii

96 2A 1 b i ii
1b i Draw the Maxwell-Boltzmann curves for the distribution of molecular speeds at two different temperatures for an
ideal gas.
2
Plot of Boltzmann distribution curve at two temperatures T
1
and T
2
, where T
2
> T
1


(½ marks for correct shape of the curves; ½ marks for indicating T
2
> T
1
)

ii Use your curves in (i) to explain why, for a fixed mass of an ideal gas at constant volume, the pressure increases
as the temperature is raised.
2
As temperature increases, fraction of molecules with high average speed / kinetic energy increases. 1 mark
Hence, force exerted by the collision of molecules on the container wall / the chance in momentum of molecules
upon collision / frequency of collision increases. 1 mark


98 2A 3 b i ii
3b The exothermic reaction
E(g) → E'(g) (1)
is a single stage reaction.

i Sketch curves to show the distribution of molecular kinetic energy of the reactant, E(g), at two different
temperatures.

ii With reference to your answer in (i), explain why the rate of reaction (1) increases with temperature.

III. Collision theory and activation energy Unit 2 Page 1
Topic III. Collision theory and activation energy Unit 2

Reference
Reading

5.4
A-Level Chemistry Syllabus for Secondary School (1995), Curriculum Development Council, 199–200

Reading
Assignment

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 312
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 413–414
Advanced Practical Chemistry, John Murray (Publisher) Ltd., 100–101
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 365, 367–368

Syllabus

Determination of activation energy

Notes
B. Determination of activation energy

By rearranging the Arrhenius equation, the activation energy of a particular reaction can be determined
experimentally.


k = Ae
E
RT
A



ln k = ln Ae
E
RT
A



ln k = ln A + ln e
E
RT
A



ln k = ln A -
E
A
RT
ln e

ln k = ln A -
E
A
RT
where ln e = 1



1. By measuring the rate of reaction at different temperature

Rate ∝ k


Rate
1
Rate
2
=
k
1
k
2


By measuring the rate of reaction at 2 different temperature, 2 set of data – Rate
1
, T
1
and Rate
2
, T
2
can be obtained.

ln k
1
= ln A -
E
A
RT
1
Eq. 1
ln k
2
= ln A -
E
A
RT
2
Eq. 2

Eq. 1 - Eq. 2 ln k
1
- ln k
2
= (ln A -
E
A
RT
1
) - (ln A -
E
A
RT
2
)

ln
k
1
k
2
= -
E
A
R
(
1
T
1
-
1
T
2
)

ln
Rate
1
Rate
2
= -
E
A
R
(
1
T
1
-
1
T
2
)


By putting the Rates and temperature determined, R = 8.314 J
-1
K
-1
mol
-1
. The activation energy, E
A
, can be
determined.

III. Collision theory and activation energy Unit 2 Page 2


2. By plotting graph of ln k versus
1
T

To be more accurate, A and E
A
can then be determined by plotting a graph with ln k versus
1
T




k at different temperature can be determined by
measuring the rates of a reaction at different
temperatures according to the integral form of rate
equation. (Refer to order of reaction and rate constant).



3. By plotting graph of ln rate versus
1
T


Actually, it is very time consuming to use plotting of ln k versus
1
T
to determine the activation energy. In order to
determined a value of k at a certain temperature, a set of values of rate / concentration have to be determined first.
(Refer to order of reaction and rate constant). To determine the E
a
, many sets of values of rate / concentration at
different temperature have to be measured.

Since

Rate ∝ k and k = Ae
E
RT
A



Rate ∝ Ae
E
RT
A



Rate = rAe
E
RT
A

r : a proportionality constant
Rate = qe
E
RT
A

q : another proportionality constant = rA

ln rate = ln qe
E
RT
A



ln rate = ln q + ln e
E
RT
A



ln rate = ln q -
E
A
RT
ln e

ln rate = ln q -
E
A
RT
where ln e = 1

ln rate = ln q -
E
A
R

1
T


By plotting a graph ln rate versus
1
T
, the slope of the graph will equal to -
E
A
R
.

This provides a more convenient way to determine the activation energy if the determination of the Arrhenius
constant is not required.
III. Collision theory and activation energy Unit 2 Page 3

Glossary
Arrhenius equation

Past Paper
Question
91 2A 3 a i ii
92 1A 2 e
93 2A 2 a
94 2A 1 c iii
96 1A 1 b iii
97 2A 3 d
98 2A 3 a i

91 2A 3 a i ii
3a For the reaction 2XY
(g)
→ X
2(g)
+ Y
2(g)
, the rate constant is 3.91 × 10
-4
mol
-1
dm
3
s
-1
at 370ºC and 4.05 × 10
-2
mol
-
1
dm
3
s
-1
at 470ºC.
Generally the rate constant of a reaction is related to the temperature by k = A exp(-E
a
/RT).
Calculate

i the activation energy, 4

ln ln k A
E
RT
a
= −
ln
k
k
E
R
(
1
T
1
T
)
T
T
a
1 2
2
1
= − 1 mark
T
1
= 273 + 370 = 643 K
T
2
= 273 + 470 = 743 K ½ mark
ln
.
. .
( )
4 05 10
391 10 8 31
1
643
1
743
2
4
×
×
= +


E
a
½ mark
E
a
= 184.2 kJmol
-1
(wrong unit -½) (not 3-4 sig.fig. -½) 2 marks

ii the rate constant at 450ºC
(Gas constant, R = 8.31 JK
-1
mol
-1
)
2
450 ºC ≡ 723 K
ln(
.
)
.
.
( )
k
723
4
3
391 10
184 2 10
8 31
1
643
1
723 ×
=
×



k
723
= 1.77 × 10
-2
mol
-1
dm
3
s
-1
(wrong unit -½) 2 marks

C i Some candidates were not familiar with calculations involving the use of natural logarithm.
ii Some weaker candidates failed to realize that the absolute temperature should be used in the calculation.

92 1A 2 e
2e The diagram below gives the Maxwell-Boltzmann energy distribution of a system of molecules at two
temperatures:

What do the shaded areas of the curves represent and why are they different at different temperatures?
2
These curves plot the distribution of molecular kinetic energies at different temperatures. It is intended to reflect
that the most sensitive parameter which affects the reaction rate is the activation energy, E
a
. ½ mark
The shaded area under either one of these curves corresponds to E ≥ E
a
and is approximately equal to the fraction
of molecules that collide with kinetic energy ≥ E
a
. ½ mark
The increase of the reaction rate with temperature corresponds closely to the ratio of the corresponding areas
where E
a
represents the minimum collision energy necessary for the reaction to occur. ½ mark
Therefore, as the temperature changes, the area under the distribution curve for E ≥ E
a
changes. ½ mark

C The poor performance to the first part of this question was disappointing. This is a standard question which has
appeared almost on a yearly basis, yet candidates continued to fail to clearly explain the meaning of the various
features of the Maxwell-Boltzmann distribution curve.


III. Collision theory and activation energy Unit 2 Page 4
93 2A 2 a
2a Discuss, in terms of the Arrhenius equation, the effect of temperature on the rate of a reaction. 2
The rate of reaction is normally increased by raising the temperature. 1 mark
Arrhenius Equation: ln k = -
E
a
RT
+ C or k = Ae
E
RT
a


Increase in T makes
1
T
smaller and -
E
a
RT
larger, hence ln k (k) increases. 1 mark


94 2A 1 c iii
1c The table below lists the concentration of the reactant C as a function of time at 298 K for the following reaction.
C → D
Time / s 0 60 120 180 240 300
[C] /10
-2
mol dm
-3
20.0 16.1 13.5 11.6 10.2 9.1

(Gas constant R = 8.31 JK
-1
mol
-1
)

iii The rate constant of the above reaction is found to be doubled when the temperature is raised from 298 K to 306
K. Determine the activation energy of the reaction.
2
Arrhenius Equation
ln k = C -
E
a
RT

(1) ln k = C -
E
a
R
(
1
298
)
(2) ln k + ln 2 = C -
E
a
R
(
1
306
)
(2) - (1) ln 2 =
E
a
R
(
1
298
-
1
306
) 1 mark
E
a
= 65.7 kJ (no unit -½ mark) 1 mark


96 1A 1 b iii
1b Carbon-14,
14
C, is radioactive, emitting β-particles.
iii All radioactive decay has zero activation energy. Comment on the effect of temperature upon the rate of decay. 1
According to Arrhenius Equation, rate of decay is independent of temperature. 1 mark

97 2A 3 d
3 The reaction of iodine with propanone in acidic solutions can be represented by the following equation
I
2(aq)
+ CH
3
COCH
3(aq)
→ CH
2
ICOCH
3(aq)
+ H
+
(aq)
+ I
-
(aq)


3d For a given set of initial concentrations the initial rate doubles when temperature is increased from 298 K to 308
K. Calculate the activation energy of the reaction.
2

98 2A 3 a i
3a The table below lists the rate constants, k, at different temperatures, T, for the first order decomposition of a
dicarboxylic acid, CO(CH
2
CO
2
H)
2
, in aqueous solution :
CO(CH
2
CO
2
H)
2(aq)
→ CH
3
COCH
3(aq)
+ 2CO
2(g)

9
T / K 273 293 313 333 353
k / s
-1
2.46 × 10
-5
4.75 × 10
-4
5.76 × 10
-3
5.48 × 10
-2
?
i Determine the activation energy for the reaction by plotting an appropriate graph.

IV. Energy profile of reaction Unit 1 Page 1
Topic IV. Energy profile of reaction Unit 1

Reference
Reading

5.5

Reading
Assignment

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 313–315
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 417–420
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 373–375

Syllabus

Energy profile
Transition state
Reaction mechanism
Rate determining step

Notes
Consider the reaction between bromide and bromate(V) ion

5Br
-
(aq)
+ BrO
3
-
(aq)
+ 6H
+
(aq)
→ 3Br
2(aq)
+ 3H
2
O
(l)


Kinetic studies show that this is an overall fourth order reaction.

Rate = k[Br
-
][BrO
3
-
][H
+
]
2


The theory of collision and activation energy cannot account for the order of the reaction determined.


IV. Energy profile of reaction

During a reaction, bonds are in the process of making and breaking. The idea of transition state (activated complex)
comes from an assumption that in any reaction, the reacting molecules/ions, if acquired sufficient energy to
overcome the energy barrier, would first form a transition state. The reaction would then continue to proceed as the
transition state, which is energetically unstable, immediately decompose to form the desired products.

Consider a simple reaction of hydrolysis of 1-bromobutane in aqueous alkaline solution, as it proceeds via the
following mechanism:




A. Transition state

Transition state is an activated complex at the top of
the potential curve, which is so unstable and can never
be isolated.

In the hydrolysis of 1-bromobutane, the transition state
is a pentavalent trigonal bipyramidal complex. The
transition state is highly unstable having 10 valence
electrons.

Activation energy (E
a
) – the energy difference between
the reactant and the transition state (the threshold
energy level leading to a reaction)


The energy profile for the reaction can be depicted as
follows.

IV. Energy profile of reaction Unit 1 Page 2


1. Order of reaction leads to interpretation of reaction mechanism at molecular level

Hydrolysis of 1-bromobutane is a second order reaction, the rate of reaction is directly proportional to the
concentration of OH
-
(aq)
ion and concentration of 1-bromobutane.

Rate ∝ [OH
-
][CH
3
CH
2
CH
2
CH
2
Br]

Rate = k[OH
-
][CH
3
CH
2
CH
2
CH
2
Br]

It is proposed that the transition state is formed upon the collision between a OH
-
particle and a
CH
3
CH
2
CH
2
CH
2
Br.
Since the formation involves only 1 OH
-
particle and 1 CH
3
CH
2
CH
2
CH
2
Br molecule, the rate of formation of the
transition state is directly proportional to [OH
-
] and [CH
3
CH
2
CH
2
CH
2
Br].

Hydrolysis of 1-bromobutane is called a bimolecular nucleophilic substitution reaction (S
N
2 reaction), since the
formation of the transition state involves 2 molecules. The molecularity of the reaction is said to be 2.

N.B. Molecularity is not the same as order the reaction. Molecularity is the number of the molecule involved in
the formation of the transition state in a step of the reaction. While, order of reaction is the sum of the
power of the concentration terms in the rate equation. They may or may not have the same value but their
meaning are indeed different.


a) Multisteps reaction

(1) Alkaline hydrolysis of 2-chloro-2-methylpropane

Alkaline hydrolysis of 2-chloro-2-methylpropane is found to be a first order reaction.

C
CH
3
CH
3
CH
3
Cl C
CH
3
CH
3
CH
3
OH OH
-
(aq)
Cl
-
(aq)
+ +
Rate = k[(CH
3
)
3
CCl]

It is very clear that the reaction is not a S
N
2 reaction and OH
-
ion is not involved in the formation of the transition
state. Indeed, it is a multisteps reaction consists of 2 steps


Step 1 (slow)

Cl
- C
CH
3
CH
3
CH
3
+ C
CH
3
CH
3
CH
3
Cl +

Step 2 (fast)

C
CH
3
CH
3
CH
3
+ -
OH C
CH
3
CH
3
CH
3
OH


As formation of the transition state
for step 1 involves a higher
activation energy E
a
’, the step 1
would be slower and known as the
rate determining step.

The reaction is called unimolecular
nucleophilic substitution (S
N
1
reaction) because only 1 molecule is
involved in the formation of the
transition state of the slowest step.

The reaction, therefore, is only first
order with respect to (CH
3
)
3
CCl.

C
CH
3
CH
3
CH
3
+
is called a carbocation or carbonium ion. It is an intermediate of
this reaction. Because it is at the bottom of a potential well, unlike the
highly unstable transition state, it is possible to isolate the intermediate from
the reaction mixture.
IV. Energy profile of reaction Unit 1 Page 3


(2) Reaction between bromide and bromate(V) in acidic medium

For the reaction, 5Br
-
(aq)
+ BrO
3
-
(aq)
+ 6H
+
(aq)
→ 3Br
2(aq)
+ 3H
2
O
(l)


Rate = k[Br
-
][BrO
3
-
][H
+
]
2


If the transition state is formed by collision between Br
-
, BrO
3
-
and 2 H
+
particles, the reaction rate would be
extremely slow. The probability of having four particles collide at the same time is extremely low.



b) Rate determining step


For multisteps reaction, the rate of reaction is only
controlled by the step with the slowest rate.

The step with the slowest rate is called the rate
determining step. Since the rate of the reaction is
independent of the other steps.

It is proposed that the reaction between bromide and
bromate(V) in acidic medium involves 5 steps.

Step 1 H
+
+ Br
-
→ HBr Fast
Step 2 H
+
+ BrO
3
-
→ HBrO
3
Fast
Step 3 HBr + HBrO
3
→ HBrO + HBrO
2
Slow
Step 4 HBrO
2
+ HBr → 2HBrO Fast
Step 5 HBrO + HBr → H
2
O + Br
2
Fast



Since Step 3 is the slowest step, it would be the rate determining step.

Rate of reaction ∝ [HBr][HBrO
3
]

[HBr] ∝ rate of formation of HBr ∝ [H
+
][Br
-
]

[HBrO
3
] ∝ rate of formation of HBrO
3
∝ [H
+
][BrO
3
-
]

Therefore rate of reaction ∝ [HBr][HBrO
3
]
∝ ([H
+
][Br
-
])([H
+
][BrO
3
-
])
∝ [Br
-
][BrO
3
-
][H
+
]
2


Rate = k[Br
-
][BrO
3
-
][H
+
]
2


N.B. For the concentration of HBr, the rate of disappearing of HBr in Step 4 and 5 need not to be considered.
Since Step 4 and 5 is following the rate determining step. The rate of Step 4 and 5 would only be the
same as Step 3.

IV. Energy profile of reaction Unit 1 Page 4


2. Energetic stability and kinetic stability



The reaction N
2(g)
+ 3H
2(g)
→ 2NH
3(g)
is exothermic.

N
2(g)
+ 3H
2(g)
→ 2NH
3(g)
∆H = -92 kJmol
-1
.

However, N
2(g)
does not react with H
2(g)
at room
temperature. This is because the reaction involves a
very high activation energy, E
A
= 668 kJmol
-1
. A
mixture of N
2(g)
and H
2(g)
is said to be energetically
unstable but kinetically stable.

The high activation energy is assoicated with the high
bond energies of N≡N and H–H bond.

E(N≡N) 945.4 kJmol
-1

E(H–H) 435.9 kJmol
-1






Glossary
energy profile transition state (activated complex) reaction mechanism
bimolecular nucleophilic substitution (S
N
2) molecularity unimolecular nucleophilic substitution (S
N
1)
carbocation / carbonium ion intermediate rate determining step energetic stability
kinetic stability


Past Paper
Question
91 1A 2 b iii
93 1A 1 c i ii
94 2A 2 a iii
95 2B 4 c ii
99 2A 3 a i ii iii

91 1A 2 b iii
2b The energy profile of the reaction
A
(g)
+ B
(g)
d C
(g)

under two different catalysis X and Y are represented below.


iii Compare the effect of increasing temperature on the rate of reaction in the system. 2
↑ temp. will increase the rate of reaction of both systems, 1 mark
the % increase in rate will be large for system X 1 mark

C Many candidates discussed only one system when the question asked for the effect on each system.

IV. Energy profile of reaction Unit 1 Page 5
93 1A 1 c i ii
1c Consider the energy diagram shown below for a certain reaction which takes place with three steps.


i Which is the rate-determining step? Explain. 2
Step 3. It is the intermediate step with highest activation energy, ∴ it is the slowest step. 2 marks
ii Is the reaction endothermic or exothermic? Explain. 2
Exothermic 1 mark
since the potential energy of the products is lower than that of the reactant. i.e. ∆H is negative. 1 mark


94 2A 2 a iii
2a Given the following thermochemical data.
Reaction ∆Ho
298
/ kJ mol
-1

C (graphite) + 2H
2(g)
→ CH
4(g)
- 75.0
C (graphite) + O
2(g)
→ CO
2(g)
- 393.5
H
2(g)
+ ½O
2(g)
→H
2
O
(l)
- 285.9

iii The enthalpy change of combustion of diamond at 298K is -395.4 kJ mol
-1
. Which allotrope of carbon, diamond
or graphite, is energetically more stable? Explain why carbon does not convert from the less stable allotrope to
the more stable one at room temperature.
2
∆Ho
comb.
[C(diamond)] = - 395.4 kJmol
-1

∆Ho
comb.
[C(graphite)] = - 393.5 kJmol
-1

∴ Graphite is the relatively more stable allotrope. 1 mark
Conversion from diamond to graphite involves the rearrangement of atoms in a giant covalent network would
require a high activation energy. ∴ Conversion does not occur at room temperature. 1 mark

C Many candidates erroneously said that diamond was the more stable allotrope of carbon. This indicated that their
concept of 'energetic stability' was quite confused and/or that they could not relate the sign of enthalpy terms to
the stability of compounds.


95 2B 4 c ii
4c Consider the data given below for the hydrogen halides and answer the questions that follow.
Standard enthalpy change of formation / kJmol
-1
Bond dissociation energy / kJmol
-1

H–F -269.4 +562
H–Cl -92.8 +430
H–Br -36.8 +367
H–I +26.1 +298

ii At temperatures above 400 K, hydrogen iodide decomposes to produce violet fumes, but, hydrogen chloride and
hydrogen bromide do not decompose. Briefly explain this difference and write a balanced equation for the
decomposition of HI.
4
HI has the smallest bond dissociation energy, the activation energy for its decomposition is lowest. 2 marks
And therefore it is the most easily decomposed HX.
However, HBr and HCl do not decompose at temperature > 400 K.
From the ∆H
f
values, HI is the most unstable hydrogen halide with respect to decomposition to its elements.
1 mark
2HI
(g)
→ H
2(g)
+ I
2(g)
1 mark

C ii Based on the given information candidates should have been able to point out that HI decomposes readily at
moderately low temperatures because it has a small bond dissociation energy corresponding to a low activation
energy for decomposition. The positive and therefore the largest enthalpy change of formation amongst the
hydrogen halides means that HI is the least stable hydrogen halide with respect to decomposition into its elements.


99 2A 3 a i ii iii
3a Consider the following data for the reaction
A + B → products

Initial concentration / mol dm
-3

IV. Energy profile of reaction Unit 1 Page 6
[A] [B] Initial rate / mol dm
-3
s
-1

4.0 × 10
-2
4.0 × 10
-2
6.4 × 10
-5

8.0 × 10
-2
4.0 × 10
-2
12.8 × 10
-5

4.0 × 10
-2
8.0 × 10
-2
6.4 × 10
-5


For this reaction,
i deduce its rate equation,
ii calculate the rate constant, and
iii sketch a possible energy profile. (6 marks)

IV. Energy profile of reaction Unit 2 Page 1
Topic IV. Energy profile of reaction Unit 2

Reference
Reading

5.6


Reading
Assignment

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 296, 315–317, 446
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 414–416
Advanced Practical Chemistry, John Murray (Publisher) Ltd., 102
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 370–373

Syllabus
Effect of catalyst
Application of catalysts

Notes
B. Effect of catalyst

According to collision theory, only the collision with an energy exceeding the activation energy may lead to a
reaction.


There are 2 ways to make more particles having an
energy higher than activation energy, thus increase the
reaction rate.

1. Increase the temperature of the particle ⇒ more
particles possess an energy greater than E
a
.

2. Lower the activation energy ⇒ more particles at
the original temperature posses an energy greater
than the new E
a
'. This can be done by using of
catalyst.





1. Characteristics of catalyst

Catalyst – a regenerated reagent which modify the rate of reaction.

In general, a catalyst is chemically involved in a reaction. It is consumed in one reaction step and regenerated in a
subsequent step. It can thus be used repeatedly without undergoing any permanent changes. The following
examples can be used to illustrate this:



Using of catalyst provides an alternative multisteps reaction pathway. A lower activation energy is involved in the
rate determining step of the catalyzed reaction. Thus, catalytic reaction has a faster rate of reaction.

IV. Energy profile of reaction Unit 2 Page 2


Catalyst is usually highly specific, i.e. a particular catalyst usually can catalyze only one reaction.

Since catalyst is involved in the formation of reaction intermediate, it may be physically changed after the reaction.
e.g. from granule form to powder form.

As ∆H remains unchanged, the equilibrium constant K of the reaction is not changed. The catalyst does not change
the equilibrium position of a reaction. It speeds up both forward and reverse reaction for the same extent.

Note : It can be proved that ln K = constant -
∆H
RT


Catalyst speeds up a reaction but has no effect on the yield of the reaction.




2. Theory of catalyst

According to the physical state, catalysts can be classified into 2 categories.
1. Homogeneous catalyst – the catalyst has the same physical state as the reaction mixture
2. Heterogeneous catalyst – the catalyst has different physical state from the reaction mixture


a) Homogeneous catalysis

Example 1
Acid-catalysed esterification (will be further elaborated in organic chemistry)

Esterification

R' C
O
-
O H
O
H
R
+
R O H
R' C
O
O H
alcohol
carboxylic acid
charge separation
involved
r.d.s.
R' C
O
-
O H
O R
H
+
H
2
O + R' C
O
O R
ester water


In esterification, the nucleophilic oxygen atom on alcohol is added to the carbonyl carbon. It can be seen that an
intermediate with charge separation in the structure is involved. This makes the reaction have a high activation
energy, thus, a rather slow rate.

Then, the proton possessed by the alcohol is shifted to the hydroxyl group to convert it to a better leaving group,
water H
2
O.

In contrast , esterification in the presence of any aqueous acid is found to be catalyzed.

Acid Catalyzed Esterification
C
O
R OH
H
+
f
C
O
R OH
H
O H
R'
+
f C
O
R OH
H
+
H
O R'
r.d.s.
no charge
separation involved
C
O
R OR'
H
2
O H
+
+ +
f +
C
O
R O
H
O
R'
H
H
f


In the acid catalyzed pathway, the carbonyl oxygen is first protonated. This activates the carbonyl group by
increasing the polarity of the C=O bond and make the carbonyl carbon more positive and more vulnerable to the
attack of the nucleophile, alcohol. Furthermore, no reaction intermediate with charge separation is involved in the
acid catalyzed mechanism and a much lower activation energy would result.
IV. Energy profile of reaction Unit 2 Page 3


Example 2
Reaction between aqueous solutions of iodide and persulphate ions:

2I
-
(aq)
+ S
2
O
8
2-
(aq)
→ I
2(aq)
+ 2SO
4
2-
(aq)


The reaction rate of the above redox reaction is rather low. This is probably because the reaction involves collision
among similarly charged particles.

Addition of Fe
3+
(aq)
or Fe
2+
(aq)
into the reaction mixture speed up the reaction considerably.

Oversimplified mechanism of the catalyzed reaction – Fe
3+
(aq)
or Fe
2+
(aq)
are served as a medium of e
-
transfer.

2Fe
3+
(aq)
+ 2I
-
(aq)
→ 2Fe
2+
(aq)
+ I
2(aq)
Fe
3+
(aq)
is consumed
2Fe
2+
(aq)
+ S
2
O
8
2-
(aq)
→ 2Fe
3+
(aq)
+ 2SO
4
2-
(aq)
Fe
3+
(aq)
is regenerated

The catalyzed reaction has a lower activation energy since the alternative pathway involves only collision between
oppositely charged particle.



b) Heterogeneous catalysis

Example 1
Decomposition of hydrogen peroxide in the presence of manganese(IV) oxide (MnO
2(s)
) catalyst

Without the presence of catalyst, hydrogen peroxide will only decompose slowly into water and oxygen.

2H
2
O
2(aq)
→ 2H
2
O
(l)
+ O
2(g)


The rate of reaction can be traced by monitoring the volume of oxygen evolved. In the presence of catalyst,
MnO
2(s)
, the rate of reaction will be increased tremendously. This reaction is usually used in the laboratory in the
preparation of oxygen.






N.B. Please note that the presence of the catalyst only affect the rate of the reaction but it has no effect on the
amount of oxygen obtained eventually.

However, in the presence of acid, the reaction will be slowed down. The acid is said to be a negative catalyst.
Beside the volume of the oxygen, the reaction can also be traced by quenching the reaction using excess acid. The
amount of H
2
O
2(aq)
can then be determined by back titrating with potassium iodide and sodium thiosulphate or
directly with KMnO
4(aq)
.

H
2
O
2(aq)
+ 2I
-
(aq)
+ 2H
+
(aq)
→ 2H
2
O
(l)
+ I
2(aq)
or 5H
2
O
2(aq)
+ 2MnO
4
-
(aq)
+ 6H
+
(aq)
→ 2Mn
2+
(aq)
+ 8H
2
O
(l)
+ 5O
2(g)

I
2(aq)
+ 2S
2
O
3
2-
(aq)
→ 2I
-
(aq)
+ 2S
4
O
6
2-
(aq)


Although the MnO
2(s)
granules used are chemically unchanged after the reaction, it will be physically changed into
powder form.
IV. Energy profile of reaction Unit 2 Page 4


3. Applications of catalysts

a) Use of catalyst in Haber process and hydrogenation



Haber process



Iron is used as the catalyst in the Haber process to speed
up the formation of ammonia. With the Fe catalyst, the
new activation energy is much lower than in the
uncatalyzed reaction. This makes the direct combination
of N
2(g)
and H
2(g)
viable.

N
2(g)
+ H
2(g)
d 2NH
3(g)





Hydrogenation of unsaturated oil


All lipids are triesters of glycerol (propan-1,2,3-triol)
and fatty acid (long chain carboxylic acid). The
difference between oil and fat are only the degree of
unsaturation of the fatty acids in the molecule.

Oil contains more unsaturated fatty acid that fat does.
Saturated carbon chain is larger than the unsaturated
one with the same length. Therefore, the van der Waals'
forces among the saturated carbon chain is stronger.
That's why fat is a solid and oil is a liquid at room
temperature.
CH
2
CH
CH
2
O
O
O
O
O
O
from
propan-1,2,3-triol
from different
fatty acids


Oil can be converted to fat by hydrogenation of the unsaturated carbon chain. This is done by bubbling H
2(g)

through oil under heat and pressure with the presence of Ni
(s)
catalyst. The hydrogenated oil formed is called
margarine.


b) Catalytic converter

All the cars imported into HK after 1 January 1993 are installed with catalytic converter. In the catalytic converter,
some pollutants from car exhaust (e.g. carbon monoxide, nitrogen monoxide and unburnt hydrocarbons) are
converted into relatively harmless substances (e.g. carbon dioxide, nitrogen and water) with the use of metal
catalysts such as platinum (or palladium) and rhodium.

2CO
(g)
+ 2NO
(g)
→ 2CO
2(g)
+ N
2(g)



The catalysts are coated on a honeycomb support to increase the surface area for better action.

IV. Energy profile of reaction Unit 2 Page 5


c) Enzymes

Enzymes are proteins that catalyse specific biochemical reactions. They are often called biological catalysts.
Enzymes obtained from yeast have long been used in the production of alcohol by fermentation. The fermentation
of glucose to form ethanol can be represented by the following equation :

C
6
H
12
O
6

enzyme
 →  2C
2
H
5
OH + 2CO
2


Nowadays, enzymes are used in various aspects such as in the manufacture of biological washing powders. These
washing powders contain enzymes which can break down stains caused by blood, egg, sweat as well as fats. They
have the advantage of removing stains even at normal temperature.



Glossary
catalyst regenerated reagent homogeneous catalysis heterogeneous catalysis adsorption
Haber process hydrogenation catalytic converter palladium rhodium enzyme


Past Paper
Question
91 1A 2 b iv
95 1A 1 e i
98 2A 3 b iii

91 1A 2 b iv
2b The energy profile of the reaction
A
(g)
+ B
(g)
d C
(g)

under two different catalysis X and Y are represented below.


iv Why could the use of a different catalyst change the order of the reaction? 2
different reaction paths or different reaction mechanisms is involved with the catalyst added. 2 marks
C In part (iv) some candidates related the order of reaction to activation energy.

95 1A 1 e i
1e The reaction between ethanoic acid and ethanol can be represented by the following equation:
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
d CH
3
COOC
2
H
5(l)
+ H
2
O
(l)

12.01 g of ethanoic acid are treated with 4.61 g of ethanol in the presence of a catalyst. When the reaction reaches
equilibrium at 298 K, 5.04 g of ethanoic acid are found to have reacted.

i Name a suitable catalyst for this reaction in the forward direction. 1
Concentrated sulphuric(VI) acid / hydrochloric acid / hydrogen chloride gas 1 mark

IV. Energy profile of reaction Unit 2 Page 6
98 2A 3 b iii
3b The exothermic reaction
E(g) → E'(g) (1)
is a single stage reaction.

iii In the presence of a catalyst, C, reaction (1) will proceed at a faster rate via the following mechanism :
E(g) + C(g) → EC(g)
EC(g) → C(g) + E'(g)
(EC is the reaction intermediate.)
Sketch labelled energy profiles for the conversion of E(g) to E'(g), with and without the catalyst. Explain why
reaction (1) proceeds faster in the presence of the catalyst.


V. Factors influencing the rate of reaction Page 1
Topic V. Factors influencing the rate of reaction

Reference
Reading

5.7


Assignment
Reading

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 293–296
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 399–401
Laboratory experiments for general, organic & biochemistry (2nd ed.), Saunders College Publishing, 187–196, 522
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 354–356

Syllabus
Factors influencing the rate of reaction

Notes
V. Factors influencing the rate of reaction

A. Concentration
The collision frequency among the particles increases with increasing concentration.

B. Temperature
Increase in temperature causes increase in energy of the particles. A larger fraction of particles will have energy
greater than E
A
. Furthermore, the collision frequency also increase.

C. Pressure
For gaseous reactant, pressure is equivalent to concentration for solution. A gas under pressure means that there are
more gaseous particle in a given volume.

D. Surface area
For solid reactant, a finer particles means a higher surface area to volume ratio. A larger surface area would lead to
more collisions per unit mass of the solid reactant and higher reaction rate.

E. Catalyst
Use of catalyst lower the activation energy E
A
, this makes a larger fraction of particles having an energy greater
than E
A
.

F. Light
Beside heat, light is also another source providing energy for the reaction.


Glossary


Past Paper
Question
90 2A 1 c

90 2A 1 c
1c Give, with explanations, two factors that would increase the rate of a reaction. 4
Temperature: An increase in temperature increases the number of particles having sufficient energy to produce
fruitful collision, and also that the average kinetic energy will be increased. This will result in
higher velocities and hence more collision per unit time. 2 marks
Concentration: An increase in concentration will give more particles per unit volume and hence more collision
per unit time. 2 marks
Catalyst: A catalyst that increases a reaction rate does so by providing a new mechanism. If the activation
energy of the limiting step of the new mechanism is lower than the activation energy of the limiting
step of the uncatalyzed reaction, then the rate is increased. 2 marks
Maximium of 4 marks for any 2 correct answers.

C Many candidates failed to point out explicitly that only in gas-phase reactions would an increase in pressure lead
to an increase in reaction rate.


Chemical Equilibria Page 1
Chemical Equilibria

I. Nature of equilibrium
A. Dynamic nature
B. Examples of equilibrium
1. Bromine water in acidic and alkaline medium
2. Potassium dichromate in acidic and alkaline medium
3. Hydrolysis of bismuth chloride
C. Equilibrium law
1. Introduction to different equilibrium constant (K) – K
c
, K
p
, K
w
, K
a
, K
b
, K
In
, K
d

2. Equilibrium constant (K
c
and K
p
)
3. Degree of dissociation (α)
4. Concentration of solid
5. Determination of equilibrium constant (K
c
)
a) Esterification
b) Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

6. Relationship between rate constant and equilibrium constant
D. Effect of change in concentration, pressure and temperature on equilibria (Le
Chaterlier's principle)
1. Concentration
2. Pressure
3. Temperature
a) Equation : ln K = constant -
∆H
T

4. Effect of catalyst on equilibria
5. Examples of calculation

Chemical Equilibria Page 2
II. Acid-base Equilibria
A. Acid-base Theory
1. Arrhenius definition
2. Bronsted-Lowry definition
3. Lewis definition
B. Strength of acid
1. Leveling effect
C. Dissociation of water
1. Ionic product of water
D. pH and its measurement
1. Definition of pH
2. Temperature dependence of pH
3. Measurement of pH
a) Use of pH meter
(1) Calibration of pH meter
b) Use of indicator
(1) Colour of indicator
E. Strong and weak acids/bases
1. Measuring of pH or conductivity of acid / base
2. Dissociation constant (K
a
and K
b
)
a) Dissociation of polybasic acid
(1) Charge effect
3. Calculation involving pH, K
a
and K
b

a) Relationship between K
a
and K
b
(pK
a
and pK
b
)
b) Relationship between pH, pOH and pK
w

c) Some basic assumptions applied
4. Experimental determination of K
a

F. Buffer
1. Principle of buffer action
a) pH of an acidic buffer
b) pH of an alkaline buffer
2. Calculation of buffer solution
G. Theory of Indicator
H. Acid-base titration
1. Difference between equivalence point and end point
2. Titration using pH meter
3. Titration using indicator
a) Choosing of indicator
4. Thermometric titration
5. Conductimetric titration
a) Strong acid vs Strong base
b) Weak acid vs Strong base
c) Weak acid vs Weak base

Chemical Equilibria Page 3
III. Redox Equilibria
A. Redox reaction
1. Balancing of redox reaction
a) By combining balanced half-ionic equation
(1) Steps of writing balanced half-ionic equation
(2) Combining half-ionic equations
b) By the change in oxidation no.
2. Faraday and mole
3. Calculation of mass liberated in electrolysis
B. Electrochemical cells
1. Measurement of e.m.f.
a) Potentiometer
b) High impedance voltmeter / Digital multimeter
2. Use of salt bridge
a) Requirement of a salt bridge
b) An electrochemical cell does not need salt bridge
3. Cell diagrams (IUPAC conventions)
C. Electrode potentials
1. Standard hydrogen electrode
2. Relative electrode potential (Standard reduction potential)
a) Meaning of sign and value
3. Electrochemical series
4. Use of electrode potential
a) Comparing the oxidizing and reducing power
b) Calculation of e.m.f. of a cell
c) Prediction of the feasibility of redox reaction
(1) Disproportionation reaction
D. Secondary cell and fuel cell
1. Lead-acid accumulator
2. Hydrogen-oxygen fuel cell
E. Corrosion of iron and its prevention
1. Electrochemical process of rusting
2. Prevention of rusting
a) Coating
b) Sacrificial protection
c) Alloying

I. Nature of equilibrium Part 1 Page 1
Topic I. Nature of Equilibrium Part 1

Reference
Reading
6.0 – 6.1.0
Practical Chemistry (3rd ed.), Heinemann, 11–12

Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 83–86, 228–229, 231
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 325–329
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 289–296

Syllabus
Nature of equilibrium
Dynamic nature

Notes
I. Nature of equilibrium

A. Dynamic nature

Equilibrium means a state of balance. There are two kinds of equilibrium : Static equilibrium and Dynamic
equilibrium.


Static equilibrium Dynamic equilibrium


The positions of the two boys remain unchanged
because they are not in motion. They are in a state of
static equilibrium.
A boy can also maintain a fixed position on a moving
escalator. This can be done by running at the same
speed of the escalator but at a different direction. The
position of the boy remains unchanged but both the
escalator and the boy are in motion. They are in a state
of dynamic equilibrium.



All equilibria studied in chemistry are dynamic in
nature.

In A-Level, we are going to study chemical equilibrium,
acid-base equilibrium, redox equilibrium and phase
equilibrium.

Chemical equilibrium includes all equilibria involving
any chemical reaction. Acid-equilibrium and redox
equilibrium are 2 examples of chemical equilibrium.

Phase equilibrium is the study of equilibrium involving
interconversion of phases.
For examples
1. Solid phase, liquid phase and gaseous phase.
2. Aqueous phase and organic phase.
3. Moving phase and stationary phase
Equilibrium
Static
equilibrium
Dynamic
equilibrium
Phase
equilibrium
Chemical
equilibrium
Acid-base
equilibrium
Redox
equilibrium


I. Nature of equilibrium Part 1 Page 2


All chemical equilibria are dynamic in nature.

Consider the following reversible reaction,


Reactant Product
forward reaction
backward reaction


Rate of forward reaction = k
1
[Reactant]
Rate of backward reaction = k
-1
[Product]


Time
C
o
n
c
e
n
t
r
a
t
i
o
n

/

m
o
l

d
m
-
3
Concentration of reactant
Concentration of product
0
Concentrations of reactant and product

At the beginning, there is only reactant but no product. Once the reaction proceeds, the concentration of the
reactant drops and the concentration of the product rises. Since the rate of reaction increases with concentrations,
the rate of the forward reaction will decrease and the rate of the backward reaction will increase.

Time
R
a
t
e

/

m
o
l

d
m
-
3

s
-
1
Rate of forward reaction
Rate of backward reaction
Rate of reaction
0


At equilibrium, forward rate = backward rate

When the increasing backward rate reaches the decreasing forward rate, there will be no net conversion between
product and reactant. The amounts of reactant and product will remain constant and an equilibrium is established.
However, the forward reaction and backward reaction do not stop after the equilibrium has established, there is
always a constant conversion between the reactant and the product. Therefore, the equilibrium is said to be
dynamic in nature.
I. Nature of equilibrium Part 1 Page 3


Consider another example





If H
2
O
(l)
is heated in a sealed pressure cooker at a constant temperature, H
2
O
(l)
vaporizes to steam H
2
O
(g)
. At the
same time, steam also condenses back to water. Eventually, the amounts of water and steam will become constant.
This system doesn’t involve any chemical change but only interconversion between liquid phase (water) and
gaseous phase (steam). This is an example of phase equilibrium.

All equilibria only exist in close systems. In the above example, no equilibrium will exit if the cover of the pressure
cooker is removed.



I. Nature of equilibrium Part 1 Page 4


B. Examples of chemical equilibrium

1. Bromine water in acidic and alkaline medium

Br
2(aq)
+ H
2
O
(l)
d HBr
(aq)
+ HBrO
(aq)

orange colourless colourless colourless

Since HBr
(aq)
is a strong acid while HBrO
(aq)
is a weak acid, the equation may be rewritten as follow :

Br
2(aq)
+ H
2
O
(l)
d H
+
(aq)
+ Br
-
(aq)
+ HBrO
(aq)

orange colourless colourless colourless colourless

In this equilibrium, Br
2(aq)
is orange in colour and all the other species are colourless.

Once the equilibrium is established, the forward rate of reaction will be the same as the backward rate of
reaction. And the concentrations of all species will remain constant.

The equilibrium can be disturbed by either addition of acid or alkaline.


Addition of acid

Br
2(aq)
+ H
2
O
(l)
d H
+
(aq)
+ Br
-
(aq)
+ HBrO
(aq)

orange colourless colourless colourless colourless


Upon addition of acid, the concentration
of H
+
(aq)
increases suddenly
accompanying with a sudden increase in
backward reaction rate.

More product is converted back to
reactant. The concentration of product
drops and the concentration of the
reactant rises.

A new equilibrium position will be
established when the concentrations of
product and reactant reaches a level that
the forward rate and the backward rate
become the same again.

At the new equilibrium position, the
concentration of product will be lower
that the original concentration while the
concentration of reactant will become
higher.




The position of the equilibrium is said to be shifted to the left by the addition of acid. And the colour of the
equilibrium mixture will become darker.


I. Nature of equilibrium Part 1 Page 5


Addition of alkali

Br
2(aq)
+ H
2
O
(l)
d H
+
(aq)
+ Br
-
(aq)
+ HBrO
(aq)

orange colourless colourless colourless colourless


Conversely, the equilibrium position can
also be shifted to the right by addition of
alkaline.

Upon addition of alkaline, the hydrogen
ions are neutralized.

H
+
(aq)
+ OH
-
(aq)
→ H
2
O
(l)


The decrease in concentration of H
+
(aq)

slows down the backward reaction.
Eventually, the equilibrium will adjust to
a new position.

The colour intensity of the equilibrium
mixture will become lighter as the
concentration of Br
2(aq)
decreases.



Questions :
What if NaBr
(s)
is added ?


2. Potassium dichromate in acidic and alkaline medium

2CrO
4
2-
(aq)
+ 2H
+
(aq)
d Cr
2
O
7
2-
(aq)
+ H
2
O
(l)

yellow colourless orange colourless


Cr
O
-
O
-
O
O
Cr
O
-
O
-
O
O
H
+
H
+
O
Cr Cr
O O
O O
O
-
O
-
+ + + + H
2
O
chromate(VI) ion dichromate(VI) ion



Upon addition of acid, the equilibrium
position can be shifted to the right and
becomes orange.

While upon addition of alkali, the
equilibrium position can be shifted to
the left and becomes yellow.
I. Nature of equilibrium Part 1 Page 6


3. Hydrolysis of bismuth chloride

BiCl
3(aq)
+ H
2
O
(l)
d BiOCl
(s)
+ 2HCl
(aq)

colourless colourless white ppt. colourless

When solid bismuth chloride (BiCl
3
) is mixed with water, a white suspension of bismuth oxychloride (BiOCl)
is formed.

Upon addition of drops of HCl
(aq)
, the white disappears and the white ppt. of bismuth oxychloride reappear
upon addition of drops of water.



Although not all reactions are reversible, it would be beneficial to consider them all reversible. And consider an
irreversible reaction only an equilibrium lying completely onto one side.

Glossary
equilibrium / equilibria static equilibrium dynamic equilibrium chemical equilibrium
acid-base equilibrium redox equilibrium phase equilibrium reversible reaction
forward rate backward rate close system shifting in equilibrium position chromate(VI) ion
dichromate(VI) ion bismuth chloride bismuth oxychloride

Past Paper
Question
92 2B 4 b i ii
98 2B 8 b i

92 2B 4 b i ii
4b i Draw the structures of the chromate(VI) and dichromate(VI) ions. 2

1 mark each

ii Write an equation showing the action of aqueous acid on the chromate(VI) ion. 1
2CrO
4
2-
+ 2H
+
d Cr
2
O
7
2-
+ H
2
O 1 mark
C i Candidates should take care in providing a 3-D diagram, which shows the correct bond orders and charge(s).
Some candidates stated that the shape of the chromate(VI) ion is square-planar.

ii the chromate(VI) - dichromate(VI) equilibrium is not a redox reaction, as stated by some candidates.

98 2B 8 b i
8b For each of the following, state the expected observation and write the relevant balanced equation(s). 6
i Dilute sulphuric(VI) acid is added dropwise to a solution of potassium chromate(VI).

I. Nature of equilibrium Part 2 Page 1
Topic I. Nature of Equilibrium Part 2

Reference
Reading

6.1.1
A-Level Chemistry Syllabus for Secondary School (1995), Curriculum Development Council, 201–202
Chemistry – Experimental foundation, Prentice Hall Inc., 51–55

Assignment
Reading

Advanced Practical Chemistry, John Murray (Publisher) Ltd., 53–56
Calculations for A-Level Chemistry, Stanley Thornes (Publishers) Ltd, 230–238
A-Level Chemistry (3
rd
ed.), Stanley Thornes (Publisher) Ltd., 86–87, 229–231, 232–233, 236–238
Chemistry in Context (4
th
ed.), Thomas Nelson and Sons Ltd., 333–340
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 296–303

Syllabus
Equilibrium law
Equilibrium constant (K
c
and K
p
)

Notes
C. Equilibrium law

1. Introduction to different equilibrium constant (K) – K
c
, K
p
, K
w
, K
a
, K
b
, K
In
, K
d


Considering the following reversible reaction

a A + b B d c C + d D

At equilibrium, it is found that the expression
[C]
c
[D]
d
[A]
a
[B]
b is a constant at a given temperature. The expression is
called equilibrium constant, denoted by the symbol K or K
eq
. The unit of K is depending on the values of
stoichiometric coefficients.

K or K
eq
=
[C]
c
[D]
d
[A]
a
[B]
b

This equation describes the relationship between the concentrations of reactant and product. The equation is
also known as Law of equilibrium or Equilibrium law.

a) Relationship between rate constant and equilibrium constant

At equilibrium, the rate of forward reaction equals the rate of backward equation. Moreover, because the
whole reaction is in equilibrium, all intermediate steps of the reaction are in equilibrium. Therefore, the rate of
reaction is no longer depending on the rate determining step only. Instead, the rate of reaction is depending on
the concentration and stoichiometric coefficients.

Forward rate at equilibrium = k
1
[A]
a
[B]
b
where k
1
is the rate constant of forward reaction
Backward rate at equilibrium = k
-1
[C]
c
[D]
d
k
-1
is the rate constant of backward reaction

Forward rate at equilibrium = Backward rate at equilibrium

k
1
[A]
a
[B]
b
= k
-1
[C]
c
[D]
d



k
1
k
-1
=
[C]
c
[D]
d
[A]
a
[B]
b = K

∴ K =
k
1
k
-1


N.B. This is applicable only if the reaction is at equilibrium. If the reaction is not at equilibrium, the
rate equation must be determined experimentally.

I. Nature of equilibrium Part 2 Page 2


There are many different kinds of expression of equilibrium constant depending on the type of equilibrium
concerned. e.g. K
c
, K
p
, K
w
, K
a
, K
b
, K
In
, K
d
.

Type Meaning Example Equilibrium Law

Chemical Equilibrium constant in
term of concentration, K
c

2CrO
4
2-
(aq)
+ 2H
+
(aq)
d Cr
2
O
7
2-
(aq)
+ H
2
O
(l)

K
c
=
[Cr
2
O
7
2-
(aq)
]
[CrO
4
2-
(aq)
]
2
[H
+
(aq)
]
2

Chemical Equilibrium constant in
term of partial pressure,
K
p

N
2(g)
+ 3H
2(g)
d 2NH
3(g)

K
p
=
p
NH
3
2
p
N
2
· p
H
2
3

Chemical Ionic product of water,
K
w

H
2
O
(l)
d H
+
(aq)
+ OH
-
(aq)
K
w
= [H
+
(aq)
][OH
-
(aq)
]

Acid-base Acidity constant, K
a

CH
3
COOH
(aq)
+ H
2
O
(l)

d H
3
O
+
(aq)
+ CH
3
COO
-
(aq)

K
a
=
[H
3
O
+
(aq)
][CH
3
COO
-
(aq)
]
[CH
3
COOH
(aq)
]


Acid-base Bascity constant, K
b

NH
3(aq)
+ H
2
O
(l)
d NH
4
+
(aq)
+ OH
-
(aq)

K
b
=
[NH
4
+
(aq)
][OH
-
(aq)
]
[NH
3(aq)
]


Acid-base Indicator constant, K
In

HIn
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ In
-
(aq)


K
In
=
[H
3
O
+
(aq)
][In
-
(aq)
]
[HIn
(aq)
]


Phase Partition coefficient /
distribution coefficient,
K
d

I
2(aq)
d I
2(hexane)

K
d
=
[I
2(hexane)
]
[I
2(aq)
]




2. Equilibrium constant (K
c
and K
p
)

The equilibrium constant K or K
eq
describes the relationship between the concentrations of reactants and
products. However, there are many different ways to express concentration.

In general,
for a solution, concentration is expressed in term of molarity.
for a gas, concentration is expressed in term of partial pressure (which is related to mole fraction).

a) Concentration of pure solid and liquid

Molarity is only one way of expressing concentration. Indeed, concentration is a very general concept
concerning the relationship between the amount of a substance and the volume occupied by that substance.

For a pure solid / liquid, the amount is usually measured in term of mass. Therefore, the concentration of a
pure solid / liquid is the equivalent to its density which is a constant at a given temperature.

Concentration of pure solid / liquid =
amount of solid / liquid
volume occupied
=
mass of solid / liquid
volume occupied
= density


Example : Calculation of the concentration of water in term of molarity at 25ºC. Given : density of water at
25ºC is 1.00 gcm
-3
= 1000.00 gdm
-3
.

Concentration of pure water in molarity

=
no. of mole of water
volume occupied
=
mass / molar mass
volume occupied


=
volume × density / molar mass
volume occupied
=
density
molar mass


=
1000.00 gdm
-3
18.0 gmol
-1 = 55.6 moldm
-3


I. Nature of equilibrium Part 2 Page 3


b) Equilibrium constant in term of concentration, K
c


Consider the following equilibrium

2CrO
4
2-
(aq)
+ 2H
+
(aq)
d Cr
2
O
7
2-
(aq)
+ H
2
O
(l)


K =
[Cr
2
O
7
2-
(aq)
][H
2
O
(l)
]
[CrO
4
2-
(aq)
]
2
[H
+
(aq)
]
2

Besides being a product, water is also the solvent in this equilibrium. Because it is in large excess comparing
with the solutes, it can be considered as a pure liquid in here.

Since the concentration of water is constant, it may be incorporated into the equilibrium constant and the
expression will become

K
[H
2
O
(l)
]
=
[Cr
2
O
7
2-
(aq)
]
[CrO
4
2-
(aq)
]
2
[H
+
(aq)
]
2 = K
c


The expression excludes the concentration of pure solid and liquid is known as K
c
, equilibrium constant in
term of concentration.

In the writing of any equilibrium constant, the concentration of a pure solid or liquid in the equilibrium
law should be excluded.


The exclusion of concentration of pure solid / liquid in an equilibrium law is not only doctrinal. It has a
significant physical meaning.

Consider a saturated sugar solution, the concentration of the solution is not depending on the amount of sugar
remains undissolved.





sugar
(s)
+ aq d sugar
(aq)



A saturated sugar solution

A saturated solution with more
undissolved sugar crystal



Consider another equilibrium,




Fe
2+
(aq)
+ Ag
+
(aq)
d Fe
3+
(aq)
+ Ag
(s)


Equilibrium mixture with less Ag
(s)

suspension

Equilibrium mixture with more Ag
(s)

suspension



It is found that the addition of extra Ag
(s)
into the mixture has no effect on the concentrations of Fe
2+
(aq)
, Ag
+
(aq)

and Fe
3+
(aq)
. Therefore, the equilibrium position is not depending on the amount of solid silver whose
concentration is constant. This fact should be reflected in the equilibrium law.

K
c
=
[Fe
3+
(aq)
]
[Fe
2+
(aq)
][Ag
+
(aq)
]


I. Nature of equilibrium Part 2 Page 4


c) Equilibrium constant in term of partial pressure, K
p


Consider the thermal decomposition of CaCO
3(s)
, CaCO
3(s)
d CaO
(s)
+ CO
2(g)



K =
[CaO
(s)
][CO
2(g)
]
[CaCO
3(s)
]


[CaCO
3(s)
]K
[CaO
(s)
]
= [CO
2(g)
] = K
c


Or if the concentration of CO
2(g)
is expressed in term of partial pressure, the equilibrium constant is known as
K
p
.

K
p
= p
CO
2(g)






Consider the Haber process, N
2(g)
+ 3H
2(g)
d 2NH
3(g)


K
c
=
[NH
3(g)
]
2
[N
2(g)
][H
2(g)
]
3

or K
p
=
p
NH
3(g)
2
p
N
2(g)
p
H
2(g)
3

I. Nature of equilibrium Part 2 Page 5


3. Degree of dissociation (α)

Sometimes, the equilibrium positions of dissociation reactions can be described by degree of dissociation.

Degree of dissociation is the percentage of molecules that undergoes dissociation and represented by α.

Consider the dissociation of carboxylic acid dimer in gaseous state,

C
O
O H
C
H
H
H H
H
H
C
H O
O
C C
O
O H
C
H
H
H 2


(CH
3
COOH)
2(g)
d 2CH
3
COOH
(g)


Consider 1 mole of dimer, the mole no. would be numerically the same as no. in percentage (i.e. mole
fraction).

Initial no. of mole 1 0
no. of mole at equilibrium 1 - α 2α
Partial pressure at equilibrium p
(CH
3
COOH)
2(g)
p
CH
3
COOH
(g)


The equilibrium law in term of partial pressure can be expressed as

K
p
=
p
CH
3
COOH
(g)
2
p
(CH
3
COOH)
2(g)


Let P be the total pressure, P = p
(CH
3
COOH)
2(g)
+ p
CH
3
COOH
(g)


Since mole fraction is related to partial pressure by the equation, mole fraction =
n
i
n
=
p
i
P


p
i
=
n
i
n
P = mole fraction × P
p
(CH
3
COOH)
2(g)
= mole fraction of (CH
3
COOH)
2(g)
× P =
1 - α
(1 - α) + 2α
P =
1 - α
1 +α
P
p
CH
3
COOH
(g)
= mole fraction of CH
3
COOH
(g)
× P =

(1 - α) + 2α
P =

1 + α
P

K
p
=
p
CH
3
COOH
(g)
2
p
(CH
3
COOH)
2(g)
=
(

1 + α
)
2
P
2

1 - α
1 + α
P
=

2
1 - α
2
P

In this equilibrium, unlike equilibrium constant K
p
, dissociation constant (α) is also depending on the total
pressure of the gaseous mixture on top of temperature.

For example,
T / K 298 303 308 313
K
p
/ Nm
-2
72.9 121.1 182.7 302


At 303 K and pressure of 1400 Nm
-2

121.1 Nm
-2
=

2
1 - α
2
× 1400 Nm
-2
α = 0.145

At 303 K and pressure of 200 Nm
-2

121.1 Nm
-2
=

2
1 - α
2
× 200 Nm
-2
α = 0.363

Thus, more carboxylic acid dimers will dissociate at a lower pressure.
I. Nature of equilibrium Part 2 Page 6


4. Determination of equilibrium constant (K
c
)

The equilibrium constant K
c
can be determined by measuring the concentrations of different species in the
equilibrium mixture. Indeed, sometimes it is not necessary to measure the concentrations of all the species.

By knowing the initial concentration of the reactant and the equilibrium concentration of the reactant or
product, the concentration of the other species can be determined according to the law of conservation of
mass.

Consider an equilibrium mixture with initial concentrations of 1 mol dm
-3
Fe
3+
(aq)
and 2 mol dm
-3
of NCS
-
(aq)


respectively.

Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

iron(III) ion thiocyanate ion thiocyanato iron(III) ion
pale yellow colour dark red complex

e.g. Initially Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

1 mol dm
-3
2 mol dm
-3
0 mol dm
-3


At equilibrium Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

(1 - x) mol dm
-3
(2 - x) mol dm
-3
x mol dm
-3


By knowing the equilibrium concentration of either Fe
3+
(aq)
, NCS
-
(aq)
or FeNCS
2+
(aq)
, the equilibrium constant
can be determined.

K
c
=
[FeNCS
2+
(aq)
]
[Fe
3+
(aq)
][NCS
-
(aq)
]
=
x
(1 - x) (2 - x)
dm
3
mol
-1


I. Nature of equilibrium Part 2 Page 7


a) Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)


First of all, equilibrium constant is a value affected by temperature. It is better to keep the temperature constant
by immersing the solution to be studied in a water bath.

For the equilibrium, Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)
, the initial concentrations of Fe
3+
(aq)
and NCS
-
(aq)
can
be determined by prepared corresponding standard solution of Fe(NO
3
)
3(aq)
and KNCS
(aq)
. The problem is how
to determine the equilibrium concentration of either Fe
3+
(aq)
, NCS
-
(aq)
or FeNCS
2+
(aq)
. If titration is used to
determine the concentration, the reaction must be quenched first. Otherwise, when the chemical is being
titrated, the equilibrium position will also be shifted.

Since FeNCS
2+
(aq)
is deep red in colour, its concentration can be determined by colorimetric measurement
without quenching. Firstly, a calibration curve which relates the concentration of FeNCS
2+
(aq)
and the colour
intensity must be constructed. This can either be done by using a calorimeter or visual comparison.



In the construction of calibration curve, samples of standard FeNCS
2+
(aq)
with various concentrations are
prepared. These are prepared by adding excess NCS
-
(aq)
into standard Fe
3+
(aq)
. It is assumed that all Fe
3+
(aq)
ions
are converted to FeNCS
2+
(aq)
. Therefore, the concentration of FeNCS
2+
(aq)
can be determined from
concentration of Fe
3+
(aq)
.

Equilibrium mixture with known initial Fe
3+
(aq)
and NCS
-
(aq)
concentrations are prepared. The equilibrium
concentration of FeNCS
2+
(aq)
in the mixture is determined by a colorimeter or by visual comparison of the
intensity of the samples prepared before. Hence, the equilibrium constant K
c
=
[FeNCS
2+
(aq)
]
[Fe
3+
(aq)
][NCS
-
(aq)
]
can be
determined. Several trials with different concentrations should be done to obtain an average value.





I. Nature of equilibrium Part 2 Page 8


b) Esterification

CH
3
COOH
(aq)
+ CH
3
CH
2
OH
(aq)
d CH
3
COOCH
2
CH
3(aq)
+ H
2
O
(l)


Both esterification and hydrolysis of ester are very slow, even in the presence of acid catalyst, it takes 48 hours
for the system to reach a state of equilibrium. Hence, the equilibrium concentration of CH
3
COOH
(aq)
can be
determined by titration even without quenching.
In this example, water is not the solvent and is not in large excess. It cannot be considered as a pure substance
and its concentration must be reflected in the equilibrium law.

K
c
=
[CH
3
COOCH
2
CH
3(aq)
][H
2
O
(l)
]
[CH
3
COOH
(aq)
][CH
3
CH
2
OH
(aq)
]


Since aqueous acid is required to catalyze the reaction, it would be more convenient to approach the problem
by treating it as a hydrolysis problem. This reduces the number of measurement of from 3 liquids (ethanoic
acid, alkanol and aqueous acid) to 2 liquids at the preparatory stage.

CH
3
COOCH
2
CH
3(aq)
+ H
2
O
(l)
d CH
3
COOH
(aq)
+ CH
3
CH
2
OH
(aq)


1
K
c
= K
c
' =
[CH
3
COOH
(aq)
][CH
3
CH
2
OH
(aq)
]
[CH
3
COOCH
2
CH
3(aq)
][H
2
O
(l)
]



Procedure

An accurately known volume of standard HCl
(aq)
is pipetted into a test tube containing known mass of
CH
3
COOCH
2
CH
3(l)
. The solution is shaken occasionally for 48 hours to ensure equilibrium is reached.

The initial amount of water is determined by subtracting the mass of HCl from the mass of HCl
(aq)
.
The initial amount of CH
3
COOCH
2
CH
3(l)
is determined by weighing.
The total no. of mole of HCl
(aq)
and CH
3
COOH
(aq)
at equilibrium are determined by titrating with standard
NaOH
(aq)
.

Experimental result

Mass of the empty test tube = 12.01 g
Mass of the empty test tube with CH
3
COOCH
2
CH
3(l)
= 16.52 g
Mass of the empty test tube with HCl
(aq)
and CH
3
COOCH
2
CH
3(l)
= 5.20 g

Volume of HCl
(aq)
added = 5.00 cm
3

Concentration of HCl
(aq)
= 1.953 moldm
-3


Calculation












I. Nature of equilibrium Part 2 Page 9

Glossary
equilibrium law / law of equilibrium equilibrium constant (K/K
eq
)
equilibrium constant in term of concentration (K
c
) equilibrium constant in term of partial pressure (K
p
)
degree of dissociation (α) dimer thiocyanate ion thiocyanato iron(III) ion calibration curve

Past Paper
Question
90 2A 1 a i ii
94 2A 1 b
95 1A 1 e ii
96 1A 1 f i ii
97 1A 2 a i
98 1A 2 c
99 2A 4 a i ii

90 2A 1 a i ii
1a Consider the following equilibrium at constant pressure:
A
2(g)
+ 3B
2(g)
d 2AB
3(g)

A mixture of 4.0 mol of A
2(g)
and 12.0 mol of B
2(g)
was placed in a vessel of volume 20.0 dm
3
, and heated to
565K. When the system had reached equilibrium, it was found that 4.0 mol AB
3(g)
was present.

i Calculate the concentration of each species at equilibrium. 1½
A
2(g)
+ 3B
2(g)
d 2AB
3(g)

Since 4 moles of AB
3
will consume 2 moles of A
2
and 6 moles of B
2

∴ at equilibrium:
[B
2
] =
12 - 6
20
=
6
20
moldm
-3
½ mark
[A
2
] =
4 - 2
20
=
2
20
moldm
-3
½ mark
[AB
3
] =
4
20
moldm
-3
½ mark

ii Calculate the equilibrium constant of this reaction at 565K. 2½

K =
[AB
3
]
2
[A
2
][B
2
]
3 = (
4
20
)
2
⋅ (
20
2
) ⋅ (
20
6
)
3
= 14.82 dm
6
mol
-2
(wrong unit -½) 2½ mark

C i Some candidates mistakenly used the initially given concentration rather than the equilibrium concentration in
their calculation of equilibrium constant.

ii Some weaker candidates failed to give the correct unit for the equilibrium constant.

I. Nature of equilibrium Part 2 Page 10
94 2A 1 b
1b A colorimetric method can be used to provide data for the determination of the equilibrium constant of the
following reaction.
Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

Outline such a method for the determination of the equilibrium constant K
c
of the above equilibrium.
4
FeNCS
2+
(aq)
ions absorb visible light in the electromagnetic spectrum / hence [FeNCS
2+
(aq)
] can be determined by
measuring the absorbance of the solution. 1 mark
Calibrate a colorimeter by measuring the absorbance of several solutions which contained known concentrations
of FeNCS
2+
(aq)
. (In these solutions, the NCS
-
ions are in excess, so that all Fe
3+
ions present can be considered as
existing in the complex form, FeNCS
2+
) 1 mark
By mixing comparable volumes of standard Fe
3+
(aq)
and NCS
-
(aq)
solutions and measuring the [FeNCS
2+
] formed
with the colorimeter, [Fe
3+
(aq)
], [NCS
-
(aq)
] and [FeNCS
2+
(aq)
] at equilibrim can be found. 1 mark
Hence, the equilibrim constant, K
c
=
[FeNCS
2
+
(aq)
]
[Fe
3+
(aq)
][NCS
-
(aq)
]
, can be determined. 1 mark

C Poorly-answered. This indicated that most candidates were not familiar with the use of a colorimetric method in
the determination of equilibrium constants. A large number of candidates did not mention the calibration of the
colorimeter.


95 1A 1 e ii
1e The reaction between ethanoic acid and ethanol can be represented by the following equation:
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
d CH
3
COOC
2
H
5(l)
+ H
2
O
(l)

12.01 g of ethanoic acid are treated with 4.61 g of ethanol in the presence of a catalyst. When the reaction reaches
equilibrium at 298 K, 5.04 g of ethanoic acid are found to have reacted.

ii Calculate the equilibrium constant, K
c
, for the reaction at 298 K. 3
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
d CH
3
COOC
2
H
5(l)
+ H
2
O
(l)


initial no. of moles
12.01
60.052

4.61
46.068
– –
= 0.2 = 0.1

no. of mole at equilibrium
12.01 - 5.04
60.052
0.1 - 0.084 0.084 0.084 2 marks
= 0.116 = 0.016

concentration at equilibrium
0.116
V

0.016
V

0.084
V

0.084
V

K
c
=
0.084
V
×
0.084
V
0.116
V
×
0.016
V
= 3.80 (no unit) 1 marks

C A common mistake in the answers was the omission of the concentration of water from the equilibrium
expression.


I. Nature of equilibrium Part 2 Page 11
96 1A 1 f i ii
1f SO
2(g)
and O
2(g)
were mixed in the mole ratio of 3 : 1 at 1000 K in the presence of a catalyst. When equilibrium
was attained at 373 kPa pressure, one half of the SO
2(g)
had been converted into SO
3(g)
.

i Write an expression for K
p
for the reaction of SO
2(g)
and O
2(g)
to give SO
3(g)
. 1

K
p
=
(P
SO
3
)
2
(P
SO
2
)
2
(P
O
2
)
or
(P
SO
3
)
(P
SO
2
)(P
O
2
)
½ 1 mark

ii Calculate K
p
for the above reaction under the given conditions. 2½
2SO
2
+ O
2
d 2SO
3

initial 3 1 0
at equilibrium 1.5 0.25 1.5 total = 3.25 ½ mark
P
SO
3
= P
SO
2
(=
1.5
3.25
× 373 kPa) ½ mark
P
O
2
=
0.25
3.25
× 373 kPa ½ mark
K
p
=
(P
SO
3
)
2
(P
SO
2
)
2
(P
O
2
)
=
1
P
O
2
=
3.25
0.25 × 373
kPa
-1
= 0.035 kPa
-1
1 mark
or, K
p
=
1
P
O
2
=
3.25
0.25 × 373
(kPa)

= 0.19 (kPa)

(1 mark)
(½ mark for numerical answer, ½ mark for unit)
(The answer and the expression (part (i)) for K
p
should be consistent with each other.)



97 1A 2 a i
2a Consider the following dissociation reaction:
PCl
5(g)
d PCl
3(g)
+ Cl
2(g)

At 400 K and 101 kPa pressure, the percentage dissociation of PCl
5(g)
is 86%.
4
i Calculate K
p
for the reaction at 400 K.

98 1A 2 c
2c At 4200 K, the equilibrium constant for the following reaction is 1.2 × 10
-2
.
N
2(g)
+ O
2(g)
d 2NO
(g)

1.0 mol of O
2(g)
and 2.0 mol of N
2(g)
are allowed to react in a 2.0 dm
3
closed container. Calculate the concentration
of N
2(g)
, in moldm
-3
. in the equilibrium mixture at 4200 K.
3

99 2A 4 a i ii
4a In the Haber process, ammonia is synthesized by the exothermic reaction of nitrogen and hydrogen at around
723K.
N
2(g)
+ 3H
2(g)
d 2NH
3(g)

In a simulation of the process, a mixture of nitrogen and hydrogen was placed in a closed container. The initial
concentrations of nitrogen and hydrogen were 0.50 mol dm
-3
and 1.50 mol dm
-3
respectively. When the
equilibrium was attained at 723 K, 25.0% of the original nitrogen was consumed.

i Calculate the respective concentrations of nitrogen, hydrogen and ammonia in the equilibrium mixture.
ii Calculate K
c
for the reaction at 723 K.

I. Nature of equilibrium Part 3 Page 1
Topic I. Nature of Equilibrium Part 3

Reference
Reading
6.1.2.0–6.1.2.4
AS-Level Chemistry Syllabus for Secondary School (1991), Curriculum Development Council, 160

Assignment
Reading

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 87, 231–232
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 343–354
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 305–309

Syllabus
Effect of change in concentration, pressure and temperature on equilibria (Le Chaterlier's principle)
Effect of catalyst on equilibria
Le Chaterlier's principle

Notes
D. Effect of change in concentration, pressure and temperature on equilibria (Le Chaterlier's principle)

1. Concentration

Br
2(aq)
+ H
2
O
(l)
d HBr
(aq)
+ HBrO
(aq)

orange colourless colourless colourless

Upon addition of extra Br
2(aq)
into the equilibrium system, some Br
2(aq)
added will be converted to HBr
(aq)
and
HBrO
(aq)
. Therefore, the net change in concentration of Br
2(aq)
is always less than the actual amount added.
Because more products are formed upon addition of the reactant, the position of the equilibrium is said to be
shifted to the right upon the addition of Br
2(aq)
.

K
c
=
[HBr
(aq)
][HBrO
(aq)
]
[Br
2(aq)
]


An increase in [Br
2(aq)
] will make the value of the expression
[HBr
(aq)
][HBrO
(aq)
]
[Br
2(aq)
]
smaller than the original K
c
.
Therefore, the equilibrium will adjust in a way to restore the expression
[HBr
(aq)
][HBrO
(aq)
]
[Br
2(aq)
]
back to the original
K
c
.

Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

iron(III) ion thiocyanate ion thiocyanato iron(III) ion
pale yellow colour dark red complex

K
c
=
[FeNCS
2+
(aq)
]
[Fe
3+
(aq)
][NCS
2+
(aq)
]


Similarly, upon addition of Fe
3+
(aq)
or NCS
-
(aq)
, the solution will turn darker. It shift the equilibrium position to
the right.
However, upon addition of Na
3
PO
4(aq)
or NaHPO
4(aq)
, the colour will get paler. PO
4
3-
(aq)
ions form complex
with free Fe
3+
(aq)
and lower its concentration. This shifts the equilibrium position to the left.

I. Nature of equilibrium Part 3 Page 2


2. Pressure

Since only gas is compressible, pressure has only effect on the equilibrium involving gaseous species.

2NO
2(g)
d N
2
O
4(g)

brown colourless





Once the plunger of the gas
syringe is pressed, the colour of
the gas gets darker because of an
immediate increase of the
concentration of brown NO
2(g)
.
However, the gas turns paler
gradually.




At equilibrium,
forward rate = backward rate
and
forward rate = k
1
[NO
2(g)
]
2

backward rate = k
-1
[N
2
O
4(g)
]

The forward reaction is a second
order reaction but the backward
reaction is only a first order
reaction. The increase in
pressure increases the forward
rate more than the backward
rate. Hence a new equilibrium
position is established
eventually.
I. Nature of equilibrium Part 3 Page 3


3. Temperature



2NO
2(g)
d N
2
O
4(g)
∆H = -58.0 kJmol
-1

brown colourless

When the tube containing the mixture of NO
2(g)
and
N
2
O
4(g)
is immersed in hot water, the colour of the
gas gets darker. Conversely, when it is put inside
icy water, the colour of the gas gets paler.





This is an exothermic reaction.

From the energy profile of the reaction, it can be
seen that the forward reaction and backward
reaction involve different activation energy. The
forward reaction has a lower activation energy Ea
1
.
i.e. Ea
1
< Ea
-1


Once the temperature is increased, the rate of both
forward reaction and backward reaction are
increased. Moreover, from the diagram of
distribution of molecular speed, the reaction with
higher activation energy will have a higher
percentage increase in rate.









∴ An increase in temperature will increase the values of k
1
and k
-1
for different extent, thus the equilibrium
constant and equilibrium position. The expression K =
k
1
k
-1
will become smaller. Therefore, a higher
temperature will shift the equilibrium position of an exothermic reaction to the left.

I. Nature of equilibrium Part 3 Page 4


a) Equation : ln K = constant -
∆H
RT


Or the effect of the temperature can be interpreted from another point of view.
It can be proved that the equilibrium constant is related to the ∆H according to the equation


∆G = ∆H - T∆S = - RTln K

where ∆G is Free energy change, which indicates the total free energy
change of the system.
T is the temperature in Kelvin.
∆H is enthalpy change of the system. It is a constant for a specific
reaction.
∆S is entropy change of the system, which is a measure of the
change in degree of disorderness. It is a constant for a specific
reaction.


N.B. Free energy change and entropy change are not required in A-Level.


(1) Derivation of ln K = -
∆H
RT
+ constant


By rearranging the equation ∆G = ∆H - T∆S = - RTln K

- RTln K = ∆H - T∆S

ln K = -
∆H
RT
+
T∆S
RT


ln K = -
∆H
RT
+
∆S
R


ln K = -
∆H
RT
+ constant

N.B. The actual derivation is not required in A-Level but you are expected to use the equation to explain
the effect of temperature on an equilibrium.
For an exothermic reaction, ∆H is negative, therefore, the expression -
∆H
RT
is positive. An increase in
temperature will make the expression -
∆H
RT
less positive, hence K will become smaller. This shifts the
equilibrium position to the reactant side.

Conversely, the equilibrium position of an exothermic reaction will be shifted to the product side if the
temperature is lowered.
I. Nature of equilibrium Part 3 Page 5


4. Effect of catalyst on equilibria

Addition of catalyst has no effect on concentrations nor equilibrium constant. Therefore, it has no effect on the
position of an equilibrium. It only increases the forward rate and backward rate for the same extent and shortens
the time required to attain equilibrium.


5. Le Chaterlier's principle

The effect of a change in condition on the position of an equilibrium can be generalized as a principle, called
Le Chaterlier's principle. Le Chaterlier's principle states that when a change is imposed on an equilibrium
system, the system will response in a way to minimize the effect of the change.

Effect of concentration
Fe
3+
(aq)
+ NCS
-
(aq)
d FeNCS
2+
(aq)

pale yellow colourless dark red

Upon addition of FeCl
3(s)
, some Fe
3+
(aq)
added with combine with NCS
-
(aq)
to form FeNCS
2+
(aq)
. As a result the
net increase of concentration of Fe3+(aq) will be reduced and the equilibrium position is shifted to the right.

If PO
4
3-
(aq)
is added to reduce the concentration of Fe
3+
(aq)
, some FeNCS
2+
(aq)
will dissociate to give more
Fe
3+
(aq)
. Consequently, the net decrease of concentration of Fe
3+
(aq)
will be reduced and the equilibrium position
is shifted to the left.


Effect of pressure

2NO
2(g)
d N
2
O
4(g)

brown colourless

Any increase in pressure can be reduced by converting 2 NO
2(g)
molecules to 1 N
2
O
4(g)
molecule Therefore,
increase in pressure will shift the equilibrium to the right.

If the pressure is decreased, the decrease in pressure can be reduced by converting 1 N
2
O
4(g)
molecule to 2
NO
2(g)
molecules.


Effect of temperature

2NO
2(g)
d N
2
O
4(g)
∆H = -58.0 kJmol
-1

brown colourless

The effect of decrease in temperature can be reduced by converting some NO
2(g)
to N
2
O
4(g)
because the
reaction is exothermic. Therefore, a decrease in temperature will shift the equilibrium position of an
exothermic reaction to the right. While a increase in temperature will shift the equilibrium position to the left.

Le Chaterlier's principle is only a rule which helps to predict the outcome of the change. In order to explain
the change, the changes in forward rate and backward rate must be considered.



Glossary
equilibrium position shifting of equilibrium position free energy change entropy change
disorderness Le Chaterlier's principle

I. Nature of equilibrium Part 3 Page 6

Past Paper
Question
91 1A 2 b i ii
92 2C 7 c
94 2A 2 b ii
95 1A 1 e iv 95 2B 4 a iii
96 1A 1 f iii
97 1A 2 a ii 97 2B 8 a iii 97 2B 8 b i

91 1A 2 b i ii
2b The energy profile of the reaction
A
(g)
+ B
(g)
d C
(g)

under two different catalysis X and Y are represented below.


i What is the effect of increasing temperature on the equilibrium of each system? 1½
↑ temp. will shift the equilibrium to the left for system X and system Y. 1½ mark
ii What is the effect of decreasing pressure on the equilibrium of each system? 1½
↓ pressure will shift the equilibrium to the left for system X and system Y. 1½ mark
C Many candidates discussed only one system when the question asked for the effect on each system. Many
candidates did not distinguish kinetics from chemical equilibria.


92 2C 7 c
7 A carboxylic acid P, with a relative molecular mass less than 100, contains C, 55.8%; H, 7.0%; and O, 37.2% by
mass . An attempt to convert P to its methyl ester Q by prolonged refluxing of P with methanol in the presence of
aqueous H
2
SO
4
gave the desired ester Q but with much of the starting material P unchanged.
(Relative atomic masses : H 1.0; C 12.0; O 16.0)

7c Suggest, with explanations, two ways which would make the esterification go towards completion. 4
The reaction is reversible 1 mark
RCOOH + CH
3
OH d RCOOCH
3
+ H
2
O 1 mark
Use large excess of CH
3
OH; mass action to shift equilibrium 1 mark
Remove H
2
O as it is formed to shift equilibrium to the right 1 mark
Use conc. H
2
SO
4
or other drying agent ½ mark

C Some candidates misunderstood the question and gave alternative synthetic routes from acid to ester. A number of
candidates failed to point out that esterification is reversible and the yield of product depends on the equilibrium
position of the reaction. Some candidates confused equilibrium and rate of reaction thinking that by changing
reaction conditions to increase the rate of reaction would make the reversible reaction go to completion.


94 2A 2 b ii
2b Account for each of the following:
ii The melting point of ice decreases with an increase in pressure. 3
In ice, the intermolecular attraction is H-bond, each H
2
O molecule is tetrahedrally surrounded by 4 other H
2
O
molecules. C.N. = 4, i.e. an open structure. 1 mark
In liquid water, the molecules are packed closer together ∴ water has a higher density than water. 1 mark
For the reaction, H
2
O
(s)
d H
2
O
(l)
, increase in pressure, shifts the equilibrium to the right ∴ m.p. of ice
decreases with increase in pressure. 1 mark


I. Nature of equilibrium Part 3 Page 7
95 1A 1 e i iv
1e The reaction between ethanoic acid and ethanol can be represented by the following equation:
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
d CH
3
COOC
2
H
5(l)
+ H
2
O
(l)

12.01 g of ethanoic acid are treated with 4.61 g of ethanol in the presence of a catalyst. When the reaction reaches
equilibrium at 298 K, 5.04 g of ethanoic acid are found to have reacted.

i Name a suitable catalyst for this reaction in the forward direction. 1
Concentrated sulphuric(VI) acid / hydrochloric acid / hydrogen chloride gas 1 mark
iv Would the addition of more of the same catalyst affect the value of K
c
? Explain. 1
No, catalyst can affect only the rate of (forward and backward reaction. 1 mark
OR
Catalyst does not affect position of an equilibrium, yield does not change. 1 mark

C A common mistake in the answers was the omission of the concentration of water from the equilibrium
expression.


95 2B 4 a iii
4a Explain the following facts:
iii Iodine is more soluble in aqueous potassium iodide solution than in water. 2
I
2
forms soluble complex I
3
-
with KI in solution. Therefore, I
2
appears more soluble. 1 mark
I
2(s)
+ KI
(aq)
d KI
3(aq)
1 mark
or I
2(s)
+ I
-
(aq)
d I
3
-
(aq)



96 1A 1 f iii
1f SO
2(g)
and O
2(g)
were mixed in the mole ratio of 3 : 1 at 1000 K in the presence of a catalyst. When equilibrium
was attained at 373 kPa pressure, one half of the SO
2(g)
had been converted into SO
3(g)
.

iii If the above reaction takes place in the absence of the catalyst, but other conditions remain unchanged, will the
value of K
p
increase, decrease or remain the same ?
½
remains the same ½ mark

97 1A 2 a ii
2a Consider the following dissociation reaction:
PCl
5(g)
d PCl
3(g)
+ Cl
2(g)

At 400 K and 101 kPa pressure, the percentage dissociation of PCl
5(g)
is 86%.
4
ii State the effect of an increase in pressure
(I) on K
p
, and
(II) on the percentage dissociation of PCl
5(g)
.


97 2B 8 a iii
8a Suggest how the following nitrogen oxides can be prepared in the laboratory. In each case, state the reactant(s)
used and the reaction conditions, and write balanced equation(s) for the reaction(s) involved.
6
iii dinitrogen tetraoxide, N
2
O
4


97 2B 8 b i
8b The synthesis of ammonia using the Haber Process involves the following:
N
2(g)
+ 3H
2(g)
d 2NH
3(g)
∆Ho = -92 kJ mol
-1

7
i State the effect of a change in temperature on the reaction at equilibrium.

I. Nature of equilibrium Part 4 Page 1
Topic I. Nature of equilibrium Part 4

Reference
Reading

6.1.2.5


Assignment
Reading

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 232–238
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 335–338
Syllabus

5. Examples of calculation

Notes
N.B. Since the equilibrium law describes the relationship of the concentrations of different species in an
equilibrium system, all calculations must be based on the concentration (
n
V
) instead of the absolute
amount (n).

1. Write an equilibrium law(s) to describe the system.
2. Figure out the relationship among the equilibrium concentrations of different species, from initial
concentrations, stoichiometric coefficients and law of conservation of mass.
3. Solve the equation(s).


Example 1
H
2(g)
+ I
2(g)
d 2HI
(g)


When 46.0 g of I
2(g)
and 1.00 g of H
2(g)
are heated to equilibrium at 470ºC, the equilibrium mixture contains 1.9 g
I
2
.
(a) How may moles of each gas are present in the equilibrium mixture?
(b) Compute the equilibrium constant.
(Given : Relative atomic masses: I, 126.9; H, 1.00)

(a) 1. K
c
=
[HI
(g)
]
2
[H
2(g)
][I
2(g)
]
=
(
no. of mole of HI
(g)
V
)
2
no. of mole of H
2(g)
V
×
no. of mole of I
2(g)
V

=
no. of mole of HI
(g)
2
no. of mole of H
2(g)
× no. of mole of I
2(g)


2. initial no. of mole of I
2(g)
=
46.0 g
126.9 gmol
-1
× 2
= 0.181 mol
initial no. of mole of H
2(g)
=
1.00 g
1.00 gmol
-1
× 2
= 0.500 mol
no. of mole of I
2(g)
at equilibrium =
1.90 g
126.9 gmol
-1
× 2
= 0.0075 mol

H
2(g)
+ I
2(g)
d 2HI
(g)



initial produced used up at equilibrium

I
2(g)
0.181 mol 0.181 - 0.0075 = 0.174 mol 0.0075 mol

H
2(g)
0.500 mol 0.174 mol 0.500 - 0.174 = 0.326 mol

HI
(g)
0 0.174 × 2 = 0.348 mol 0 + 0.348 = 0.348 mol


(b) 3 K
c
=
no. of mole of HI
(g)
2
no. of mole of H
2(g)
× no. of mole of I
2(g)
=
(0.348 mol)
2
0.326 mol × 0.0075 mol
= 50
I. Nature of equilibrium Part 4 Page 2


Example 2
H
2(g)
+ I
2(g)
d 2HI
(g)


If 1.00 mole each of H
2(g)
and I
2(g)
are heated in a 30.0 dm
3
evacuated chamber to 470ºC. Using the value of K
c

from the Example 1, determine
(a) how many mole of I
2(g)
remain unreacted when equilibrium is established,
(b) the total pressure in the chamber.
(c) Now if one additional mole of H
2(g)
is introduced into this equilibrium system, how many mole of the original
iodine will remain unreacted?
(Given : Universal gas constant (R) = 0.0821 atm mol
-1
K
-1
)

(a) 1. K
c
=
no. of mole of HI
(g)
2
no. of mole of H
2(g)
× no. of mole of I
2(g)


2. Let x mole be the no. of mole of I
2(g)
consumed.


initial produced used up at equilibrium

I
2(g)
1.00 mol x mol (1.00 - x) mol

H
2(g)
1.00 mol x mol (1.00 - x) mol

HI
(g)
0 x mol × 2 2x mol


3. K
c
=
(2x)
2
(1.00 - x)(1.00 - x)
= 50


4x
2
1.00 - 2.00x + x
2 = 50 4x
2
= 50 - 100x + 50x
2
46x
2
- 100x + 50 = 0

x = 0.78 or 1.4 (rejected)

no. of mole I
2(g)
remaining = (1.00 - 0.78) mol = 0.22 mol

(b) The number of moles of gas does not change as the reaction proceeds at 470ºC; hence 2.00 mol of gas remains
at equilibrium.

PV = nRT
P =
nRT
V
=
2.00 mol × 0.0821 atm mol
-1
K
-1
× 743 K
30.0 dm
3 = 4.07 atm

(c) 1. K
c
=
no. of mole of HI
(g)
2
no. of mole of H
2(g)
× no. of mole of I
2(g)


2. Since the final equilibrium position is not depending on when the additional H
2(g)
is introduced, it can be
assumed that it is introduced with the original H
2(g)
.

Let x mole be the no. of mole of I
2(g)
consumed.

initial produced used up at equilibrium

I
2(g)
1.00 mol z mol (1.00 – z) mol

H
2(g)
(1.00 + 1.00) mol = 2.00 mol z mol (2.00 – z) mol

HI
(g)
0 z mol × 2 2z mol

3. K
c
=
(2z)
2
(2.00 - z)(1.00 - z)
= 50


4z
2
2.00 - 3.00z + z
2 = 50 4z
2
= 100 – 150z + 50z
2
46z
2
– 150z + 100 = 0

z = 0.93 or 2.3 (rejected)

no. of mole I
2(g)
remaining = (1.00 - 0.93) mol = 0.07 mol
I. Nature of equilibrium Part 4 Page 3

Glossary
equilibrium concentration stoichiometric coefficients law of conservation of mass

Past Paper
Question
90 2A 1 a i ii iii
95 1A 1 e ii iii

90 2A 1 a i ii iii
1a Consider the following equilibrium at constant pressure:
A
2(g)
+ 3B
2(g)
d 2AB
3(g)

A mixture of 4.0 mol of A
2(g)
and 12.0 mol of B
2(g)
was placed in a vessel of volume 20.0 dm
3
, and heated to
565K. When the system had reached equilibrium, it was found that 4.0 mol AB
3(g)
was present.

i Calculate the concentration of each species at equilibrium. 1½
A
2(g)
+ 3B
2(g)
d 2AB
3(g)

Since 4 moles of AB
3
will consume 2 moles of A
2
and 6 moles of B
2

∴ at equilibrium:
[B
2
] =
12 - 6
20
=
6
20
moldm
-3
½ mark
[A
2
] =
4 - 2
20
=
2
20
moldm
-3
½ mark
[AB
3
] =
4
20
moldm
-3
½ mark

ii Calculate the equilibrium constant of this reaction at 565K. 2½

K =
[AB
3
]
2
[A
2
][B
2
]
3 = (
4
20
)
2
⋅ (
20
2
) ⋅ (
20
6
)
3
= 14.82 dm
6
mol
-2
(wrong unit -½) 2½ mark

iii When the volume of the vessel was increased and the system allowed to come to a new equilibrium at the same
temperature, 9.0 mol of B
2(g)
was found to be present. Calculate the new volume.
3
At new equilibrium: 9 moles of B
2
is present.
Let V be the new volume
[B
2
] =
9
V
½ mark
[A
2
] =
4-1
V
=
3
V
½ mark
[AB
3
] =
2
V
½ mark
K = 14.82 = (
2
V
)
2
⋅ (
V
3
) ⋅ (
V
9
)
3
½ mark
V =
14.82 × 9
3
× 3
4
= 90 dm
3
1 mark

C i Some candidates mistakenly used the initially given concentration rather than the equilibrium concentration in
their calculation of equilibrium constant.

ii Some weaker candidates failed to give the correct unit for the equilibrium constant.

95 1A 1 e ii iii
1e The reaction between ethanoic acid and ethanol can be represented by the following equation:
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
d CH
3
COOC
2
H
5(l)
+ H
2
O
(l)

12.01 g of ethanoic acid are treated with 4.61 g of ethanol in the presence of a catalyst. When the reaction reaches
equilibrium at 298 K, 5.04 g of ethanoic acid are found to have reacted.

ii Calculate the equilibrium constant, K
c
, for the reaction at 298 K. 3
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
d CH
3
COOC
2
H
5(l)
+ H
2
O
(l)


initial no. of moles
12.01 g
60.052 gmol
-1
4.61 g
46.068 gmol
-1 – –
= 0.2000 mol = 0.100 mol

no. of mole at equilibrium
12.01 - 5.04
60.052
0.100 - 0.084 0.084 0.084 2 marks
= 0.116 = 0.016

concentration at equilibrium
0.116
V

0.016
V

0.084
V

0.084
V


I. Nature of equilibrium Part 4 Page 4
K
c
=
0.084
V
×
0.084
V
0.116
V
×
0.016
V
= 3.80 (no unit) 1 marks
iii What additional mass of ethanol would be required in order to use up a further 0.60 g of ethanoic acid ? 2
0.60 g of ethanoic acid ≡ 0.010 mole
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
d CH
3
COOC
2
H
5(l)
+ H
2
O
(l)

no. of mole at equilibrium 0.0106 x 0.094 0.094 1 mark

3.80 =
0.094
2
0.106 x

∴ x = 0.0219 mole ½ mark
Need to add 0.016 mole of ethanol = 0.74 g ½ mark

C iii A common mistake in the answers was the omission of the concentration of water from the equilibrium
expression.
Few candidates were able to complete part (iii).


II. Acid-base Equilibria Part 1 Page 1
Topic II. Acid-base Equilibria Part 1

Reference
Reading
6.2.1–6.2.2


Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 255–258
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 219–222, 365–367, 369–370
Chemistry in Context (5th ed.), Thomas Nelson and Sons Ltd., 198–201, 326

Syllabus
Acid-base Equilibria
Acid-base Theory
Dissociation of water

Notes
II. Acid-base Equilibria


A. Acid-base Theory

At the early stage of development of acid-base theory, acid was only
described as a sour substance. And base is only a substance which neutralizes
the sour taste of an acid.

Nevertheless, scientists find that acids and bases bear some other properties.
According to these properties, they developed a series of definitions to
describe acid and base. They are called Arrhenius definition, Brønsted Lowry
definition and Lewis definition. The coverage of the latter definition is
boarder than the former one.

Common
Sense
A
r
r
h
e
n
i
u
s d
e
f
i
n
i
t
i
o
n
B
r
φ
n
s
t
e
d

L
owry

d
e
f
i
n
i
t
i
o
n
L
e
w
is defin
it
i
o
n


1. Arrhenius definition

Arrhenius definition is based on ionization. In 1884, Swedish chemist Svante Arrhenius proposed that

Acid – a hydrogen-containing compound that, when dissolved in water, produces hydrogen ions, H
+
(aq)
.
Base – a substance which reacts with an acid to give salt and water only.

Examples of Arrhenius acid
e.g. H
2
SO
4(l)
+ H
2
O
(l)
→ H
3
O
+
(aq)
+ HSO
4
-
(aq)

HSO
4
-
(aq)
+ H
2
O
(l)
→ H
3
O
+
(aq)
+ SO
4
2-
(aq)


Examples of Arrhenius base
e.g. NaOH
(aq)
+ HCl
(aq)
→ Na
+
Cl
-
(aq)
+ H
2
O
(l)

CuO
(s)
+ HCl
(aq)
→ Cu
2+
Cl
-
2(aq)
+ H
2
O
(l)


This is the definition used in certificate level.

Arrhenius theory is criticized that
1. Acid is restricted to hydrogen-containing species and base is restricted to oxide or hydroxide.
2. The theory is only applicable to aqueous medium where a lot of acid-base reaction takes place in the absence
of water.

II. Acid-base Equilibria Part 1 Page 2


2. Brønsted-Lowry definition

In 1923, Danish chemist Johannes Brønsted and British chemist Thomas Lowry proposed a boarder definition, in
which
Acid – a proton donor
Base – a proton acceptor

e.g. NH
3(aq)
+ H
2
O
(l)
d NH
4
+
(aq)
+ OH
-
(l)

proton proton proton proton
acceptor donor donor acceptor
(base) (acid) (conjugate (conjugate
acid of NH
3(aq)
) base of H
2
O
(l)
)

e.g. HCl
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ Cl
-
(aq)

proton proton proton proton
donor acceptor donor acceptor
(acid) (base) (conjugate (conjugate
acid of H
2
O
(l)
) base of HCl
(aq)
)

When a Brønsted-Lowry acid donates a proton, it becomes a potential proton acceptor and is called conjugate base
of the acid. Stronger a proton donor, weaker will be the conjugate base.

Similarly, when a Brønsted-Lowry base accepts a proton, it becomes a potential proton donor and is called
conjugate acid of the base. Stronger a proton acceptor, weaker will be the conjugate acid.

Water is a very special example, it can behave as both proton acceptor and proton donor. Therefore, it is a
Brønsted-Lowry acid and a Brønsted-Lowry base.

e.g. H
2
O
(l)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ OH
-
(aq)

proton proton proton proton
acceptor donor donor acceptor
(base) (acid) (conjugate (conjugate
acid of H
2
O
(l)
) base of H
2
O
(l)
)

The above reaction is also known as self-dissociation / self-ionization of water.
All Arrhenius acids and bases can be classified into Brønsted-Lowry acid and base accordingly.


3. Lewis definition

The American chemist Gilbert N. Lewis (1923) proposed an even broader definition for acid and base. He
proposed that

Acid – an electron acceptor
Base – an electron donor

This definition offers many advantages, including
i. The acids are not limited to compounds containing hydrogen.
ii. It works with solvents other than water.
iii. It does not require formation of a salt or an acid-base conjugate pair.

Since all chemical species are potential electron acceptor or electron donor, virtually, all chemical species are either
Lewis acid or Lewis base.

e.g. H
3
N:
(g)
+ BF
3(g)
→ H
3
N

BF
3(s)

electron electron
donor acceptor
(Lewis base) (Lewis acid)

Most of the chemical reaction is caused by redistribution of electrons which leads to rearrangement of atoms and
formation of a new substance. Therefore, all kinds of reaction can be considered as Lewis acid-base reaction.
Concept of Lewis acid-base is very useful in describing reaction mechanisms.
II. Acid-base Equilibria Part 1 Page 3


N.B. In the description of an acid-base equilibrium in A-Level, the Brønsted-Lowry definition is used.
However, in the description of reaction mechanism, Lewis definition is used.


B. Strength of acid

Strength of an acid can be measured by an equilibrium constant called acidity constant or acid dissociation
constant, K
a
.

For an acid, HA
(aq)
in water

HA
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ A
-
(aq)
Equilibrium constant, K
eq
=
[H
3
O
+
(aq)
][A
-
(aq)
]
[HA
(aq)
][H
2
O
(l)
]


Acidity constant, K
a
is defined as

K
a
=
[H
3
O
+
(aq)
][A
-
(aq)
]
[HA
(aq)
]
= K
eq
[H
2
O
(l)
] where [H
2
O
(l)
] is a constant since water is the solvent in large excess.

For a stronger acid, more HA
(aq)
molecules will dissociate into H
3
O
+
(aq)
ion and A
-
(aq)
ion and give a larger value for
K
a
.

Similar to pH, K
a
can also be expressed in a negative log scale.

pH = - log [H
+
] A low pH means a high concentration of H
+
ion.

pK
a
= - log K
a
A low pK
a
means a larger value for K
a
and a stronger acid.


Relative strength of selected acids and their conjugate bases




Stronger an acid, weaker will be its conjugate
base.
Stronger a base, weaker will be its conjugate
acid.


N.B.
Redox reaction can be considered as a
competition for electron.

oxidizing agent + e
-
d reducing agent

In redox reaction, only strong oxidizing agent
reacts with strong reducing agent.


Similarly, acid base reaction can be considered
as a competition for proton.

conjugate base + H
+
d conjugate acid

In acid base reaction, only strong acid react
with strong base.


The strength of an acid or a base is also an indicator of their stability. A strong acid or base is less stable than
a weak acid or base. A strong acid tends to react with a strong base to form a weak conjugate base and weak
conjugate acid.

e.g. NH
2
-
+ HC≡CH → NH
3
+ HC≡C
-
but not NH
3
+ HC≡C
-
→ NH
2
-
+ HC≡CH
II. Acid-base Equilibria Part 1 Page 4


1. Leveling effect

Acids stronger than hydroxonium ion H
3
O
+
(aq)
, do not show any difference in acidity in water. The water will
convert all those acid molecules into H
3
O
+
(aq)
ions.

HCl
(aq)
+ H
2
O
(aq)
→ H
3
O
+
(aq)
+ Cl
-
(aq)

strong strong weak weak
acid base acid base

HBr
(aq)
+ H
2
O
(aq)
→ H
3
O
+
(aq)
+ Br
-
(aq)

strong strong weak weak
acid base acid base

This is why we consider all HCl
(aq)
, H
2
SO
4(aq)
and HNO
3(aq)
are strong acid though they don't have the same
strength.

Similarly, a base stronger than hydroxide ion does not exist in aqueous medium. The water will convert all those
base molecules into OH
-
(aq)
ions. For example, NaNH
2(s)
is a very strong base, a non-aqueous solvent (e.g. liquid
NH
3(l)
) must be used.

NaNH
2(s)
+ H
2
O
(l)
→ Na
+
(aq)
+ OH
-
(aq)
+ NH
3(aq)


This is known as the leveling effect of solvent.


C. Dissociation of water

Pure water is found to be a poor conductor of electricity but not an insulator. Therefore, it must contain a very
small amount of ions. Indeed, the ions are from self-dissociation / self-ionization of water molecule.

H
2
O
(l)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ OH
-
(aq)
or simply H
2
O
(l)
d H
+
(aq)
+ OH
-
(aq)


K =
[H
+
(aq)
][OH
-
(aq)
]
[H
2
O
(l)
]


1. Ionic product of water

H
2
O
(l)
d H
+
(aq)
+ OH
-
(aq)


K =
[H
+
(aq)
][OH
-
(aq)
]
[H
2
O
(l)
]


In aqueous medium, H
2
O
(l)
is in large excess, thus [H
2
O
(l)
] is a constant and can be incorporated in the equilibrium
constant.

K [H
2
O
(l)
] = [H
+
(aq)
][OH
-
(aq)
] = K
w


K
w
is known as ionic product of water. Like other equilibrium constant, it is a quantity depending on temperature
and has the value of 1.00 × 10
-14
mol
2
dm
-6
at 25ºC.


Pure water is neutral because the concentration of H
+
(aq)
is the same as the concentration of OH
-
(aq)
.
i.e. [H
+
(aq)
] = [OH
-
(aq)
]



Acidic

Neutral

Alkaline
II. Acid-base Equilibria Part 1 Page 5


For pure water at 25ºC

K
w
= [H
+
(aq)
][OH
-
(aq)
] = [H
+
(aq)
]
2
= 1.00 × 10
-14
mol
2
dm
-6


[H
+
(aq)
] = 1.00 × 10
-7
moldm
-3


Recall that pure water has the concentration of 55.6 moldm
-3
.

[H
+
(aq)
]
[H
2
O
(l)
]
=
1.00 × 10
-7
moldm
-3
55.6 moldm
-3 = 1.80 × 10
-9


This means that only 1 out of every 556,000,000 (
1
1.80 × 10
-9 ) water molecule will dissociate into a pair of H
+
(aq)

and OH
-
(aq)
. This explains the extremely low conductivity of pure water but it is not an insulator.

Glossary
acid-base equilibria Arrhenius acid-base Brønsted Lowry acid-base Lewis acid-base
conjugate acid-base proton donor / acceptor electron acceptor / donor
acidity constant / acid dissociation constant (K
a
) pH pK
a
leveling effect
self- dissociation / self-ionization of water ionic product of water (K
w
)

Past Paper
Question
94 1A 1 f i 94 1A 2 c i ii
97 2A 4 c i
99 1A 4 a

94 1A 1 f i
1f i Write an equation to show that HPO
4
2-
(aq)
can act as a Brφnsted base in water. 1
HPO
4
2-
(aq)
+ H
2
O
(l)
d H
2
PO
4
-
(aq)
+ OH
-
(aq)
1 mark

94 1A 2 c i ii
2c i What is a “Brφnsted acid”? 1
“Brφnsted acid” is a proton donor 1 mark
ii Write equations to show that nitric(V) acid is an acid in water, but a base in liquid hydrogen fluoride. 2
HNO
3
+ H
2
O d H
3
O + NO
3
-
1 mark
HNO
3
+ HF d H
2
NO
3
+
+ F
-
1 mark

C i Many candidates thought that an aqueous medium was required for the proton donation.
ii The equation for nitric(V) acid acting as an acid was given correctly, but few candidates gave the correct equation
for it acting as a base.


97 2A 4 c i
4c A solution is formed by mixing equal volumes of 0.20 M CH
3
CO
2
H
(aq)
and 0.20 M CH
3
CO
2
Na
(aq)
.
i Identify all Brφnsted acids and all Brφnsted bases in the solution.

99 1A 4 a
4a Write all the Bronsted acids present in aqueous ammonia.

II. Acid-base Equilibria Part 2 Page 1
Topic II. Acid-base Equilibria Part 2

Reference
Reading

6.2.3


Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 258–259, 264, 268
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 367–369
Chemistry in Context (5th ed.), Thomas Nelson and Sons Ltd., 325–329

Syllabus
pH and its measurement
Temperature dependence of pH

Notes
D. pH and its measurement

1. Definition of pH


pH is defined as the negative log of the concentration of H
+
(aq)
in molarity.

pH = - log [H
+
(aq)
]

Because it is a log scale, every 1 unit increase in pH means ten folds
decrease in the concentration of H
+
(aq)
.
pH [H
+
(aq)
]

0 1 mol dm
-3

1 0.1 mol dm
-3

2 0.01 mol dm
-3

3 0.001 mol dm
-3

4 0.0001 mol dm
-3


For pure water at 25ºC,

K
w
= [H
+
(aq)
][OH
-
(aq)
] = [H
+
(aq)
]
2
= 1.00 × 10
-14
mol
2
dm
-6


[H
+
(aq)
] = 1.00 × 10
-7
moldm
-3


pH = - log[H
+
(aq)
] = - log 1.00 × 10
-7
= 7.00

Therefore, pure water has pH 7 at 25ºC.


Find the pH of a 0.1 M HCl
(aq)
solution.
Find the pH of a 10
-8
M HCl
(aq)
solution.



2. Temperature dependence of pH


Pure water has pH 7 only at 25ºC because K
w
is temperature
dependent. The degree of dissociation of water, thus the K
w
, increases
with increasing temperature.

For example, at 50ºC, K
w
= 5.47 × 10
-14
mol
2
dm
-6


K
w
= [H
+
(aq)
][OH
-
(aq)
] = [H
+
(aq)
]
2
= 5.47 × 10
-14
mol
2
dm
-6


[H
+
(aq)
] = 5.47 × 10
-14
mol
2
dm
-6
= 2.34 × 10
-7
moldm
-3


pH = - log[H
+
(aq)
] = - log 2.34 × 10
-7
= 6.63

Therefore, water at 50 ºC has a pH 6.63.
Temperature /ºC K
w
/ mol
2
dm
-6
0 0.11 × 10
-14

10 0.30 × 10
-14

20 0.68 × 10
-14

25 1.00 × 10
-14

50 5.47 × 10
-14

100 51.3 × 10
-14




N.B. A solution is said to be neutral because the concentration of H
+
(aq)
is the same as the concentration of
OH
-
(aq)
, not because of the pH. A neutral solution has the pH 7 only at 25 ºC.



Acidic

Neutral

Alkaline
II. Acid-base Equilibria Part 2 Page 2


3. Measurement of pH

pH meter, indicator and pH paper are commonly used to determine the pH of a solution.

a) Use of pH meter


pH meter is an electronic instrument which gives the pH
value of a solution directly. However, pH meter needs to be
calibrated before use.

(1) Calibration of pH meter

pH meter is calibrated by immersing the electrode into a
buffer solution with known pH and adjusting the knob on
the pH meter.

Buffer solution is a solution whose pH is insensitive to the
addition of small amount of acid or base. For example,
blood is a buffer solution which has a constant pH of about
7.4 which is independent of the acidity of our diet.





b) Use of indicator

Indicator is a chemical which has different colour at different pH. Usually, it is a weak acid or a weak base whose
conjugate acid and conjugate base have different colours.

(1) Colour of indicator

pH value
Indicator 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
litmus | red | purple | blue |
methyl orange | red |orange| yellow |
phenolphthalein | colourless |pale pink| red |


Universal indicator / pH indicator is a mixture of several indicators. As a result, the universal indicator gives a
series of colour change at different pH instead of just 2.

pH paper is a filter paper is soaked in universal indicator.

Like other testing paper, it should be dipped into the solution to be tested and removed immediately. If the paper is
immersed in the solution, the dye will diffuse into the solution and the colour observed would be paler than the
standard.

Glossary
pH scale pH meter calibration of pH meter buffer solution indicator universal
indicator.

Past Paper
Question
94 2A 3 b i
99 1A 4 d

94 2A 3 b i
3b Account for each of the following:
i At 323K, the pH of pure water is less than 7.0. 2
The dissociation of water, 2H
2
O
(l)
d H
3
O
+
(aq)
+ OH
-
(aq)
, is an endothermic process. 1 mark
Increase in temperature, the equilibrium shifts to the right and hence [H
3
O
+
(aq)
] increases. In pure water, [H
3
O
(aq)
+
]
at 323 K is higher than that at 298 K, ∴ pH of pure water at 323 K is less than 7. 1 mark

C i Many candidates were not aware of the fact that the dissociation of water is an endothermic process. Some
candidates erroneously pointed out that the low pH of water at 323 K was caused by the dissolution of some acidic
gases.


99 1A 4 d
4d Constant boiling hydrochloric acid contains 20.2% by mass of HCl. Calculate the mass of constant boiling
II. Acid-base Equilibria Part 2 Page 3
hydrochloric acid required to prepare 1.00 dm
3
of HCl
(aq)
of pH 2.0 at 298 K.

II. Acid-base Equilibria Part 3 Page 1
Topic II. Acid-base Equilibria Part 3

Reference
Reading
6.2.4
Advanced Practical Chemistry, John Murray (Publisher) Ltd., 62–64
Modern Physical Chemistry, Bell and Hyman, 283

Assignment
Reading

A-Level Chemistry (3
rd
ed.), Stanley Thornes (Publisher) Ltd., 258–262, 273
Chemistry in Context (4
th
ed.), Thomas Nelson and Sons Ltd., 369
Chemistry in Context (5th ed.), Thomas Nelson and Sons Ltd., 329–330

Syllabus
Strong and weak acids/bases
Measuring of pH or conductivity of acid / base
Dissociation constant (K
a
and K
b
)
Calculation involving pH, K
a
and K
b


Notes
D. Strong and weak acids/bases

An acid or a base is said to be strong if the degree of dissociation is high. Usually, this is measure in term of pH,
the conductivity of the solution or the dissociation constant.

1. Measuring of pH or conductivity of acid / base


Obviously, with the same concentration, a strong
acid (HCl
(aq)
) has lower pH than a weak acid
(CH
3
COOH
(aq)
). And a strong alkali (e.g. NaOH
(aq)
)
has higher pH than a weak base (e.g. NH
3(aq)
).

Owing to the higher ionic concentration, the
conductivity of a strong acid / base is also higher
than that of a weak acid / base.

Solution pH
1 M HCl
(aq)
0
0.1 M HCl
(aq)
1
0.1 M CH
3
COOH
(aq)
3
pure water 7
0.1 M NH
3(aq)
11
0.1 M NaOH
(aq)
13
1 M NaOH
(aq)
14


2. Dissociation constant (K
a
and K
b
)

For the equilibrium,

HA
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ A
-
(aq)


K =
[H
3
O
+
(aq)
][A
-
(aq)
]
[HA
(aq)
][H
2
O
(l)
]


Since H
2
O
(l)
is in excess, its concentration can be incorporated into the equilibrium constant and the new
dissociation constant is called acidity constant K
a
.

HA
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ A
-
(aq)


K =
[H
3
O
+
(aq)
][A
-
(aq)
]
[HA
(aq)
][H
2
O
(l)
]


K[H
2
O
(l)
] =
[H
3
O
+
(aq)
][A
-
(aq)
]
[HA
(aq)
]
= K
a


e.g. CH
3
COOH
(aq)
+ H
2
O
(l)
d CH
3
COO
-
(aq)
+ H
3
O
+
(aq)


K
a
=
[CH
3
COO
-
(aq)
][H
3
O
+
(aq)
]
[CH
3
COOH
(aq)
]
= 1.7 × 10
-5
mol dm
-3



II. Acid-base Equilibria Part 3 Page 2


Similarly, the dissociation constant of a base (basicity constant K
b
) can also be defined in a similar way.

B
(aq)
+ H
2
O
(aq)
d HB
+
(aq)
+ OH
-
(aq)


K =
[HB
+
(aq)
][OH
-
(aq)
]
[B
(aq)
][H
2
O
(l)
]


K[H
2
O
(l)
] =
[HB
+
(aq)
][OH
-
(aq)
]
[B
(aq)
]
= K
b


e.g. NH
3(aq)
+ H
2
O
(l)
d NH
4
+
(aq)
+ OH
-
(aq)


K
b
=
[NH
4
+
(aq)
][OH
-
(aq)
]
[NH
3(aq)
]
= 1.8 × 10
-5
mol dm
-3




a) Dissociation of polybasic acid

Consider the dissociation of tribasic acid H
3
PO
4(aq)
in water, it dissociates in water through 3 consecutive steps.

Acid K
a
(298K)/mol dm
-3
Equilibrium
H
3
PO
4(aq)
7.9 × 10
-3
H
3
PO
4(aq)
d H
+
(aq)
+ H
2
PO
4
-
(aq)
K
a
1
=
[H
+
(aq)
][ H
2
PO
4
-
(aq)
]
[ H
3
PO
4(aq)
]

H
2
PO
4
-
(aq)
6.2 × 10
-8
H
2
PO
4
-
(aq)
d H
+
(aq)
+ HPO
4
2-
(aq)
K
a
2
=
[H
+
(aq)
][ HPO
4
2-
(aq)
]
[ H
2
PO
4
-
(aq)
]

HPO
4
2-
(aq)
4.4 × 10
-13
HPO
4
2-
(aq)
d H
+
(aq)
+ PO
4
3-
(aq)
K
a
3
=
[H
+
(aq)
][ PO
4
3-
(aq)
]
[ HPO
4
2-
(aq)
]


Phosphoric acid is a tribasic acid which is not very strong. Only 25% of the molecules dissociate in water. The
first dissociation constant K
a
1
is low. Moreover, the second dissociation constant K
a
2
is lower than the first one
and the third dissociation constant K
a
3
is even lower.

Therefore, in a solution of H
3
PO
4(aq)
, it consists of mainly water and H
3
PO
4(aq)
molecules.

Relative abundance of different species

H
2
O
(l)
>> H
3
PO
4(aq)
> H
+
(aq)
> H
2
PO
4
-
(aq)
> HPO
4
2-
(aq)
> PO
4
3-
> OH
-
(aq)


Furthermore, the dissociation constants of a tribasic acid can be expressed as :

H
3
PO
4(aq)
d 3H
+
(aq)
+ PO
4
3-
(aq)

K
a(overall)
= K
a
1
× K
a
2
× K
a
3

=
[H
+
(aq)
][ H
2
PO
4
-
(aq)
]
[ H
3
PO
4(aq)
]
×
[H
+
(aq)
][ HPO
4
2-
(aq)
]
[ H
2
PO
4
-
(aq)
]
×
[H
+
(aq)
][ PO
4
3-
(aq)
]
[ HPO
4
2-
(aq)
]

=
[H
+
(aq)
]
3
[ PO
4
3-
(aq)
]
[ H
3
PO
4(aq)
]


(1) Charge effect

For a polybasic acid, the first dissociation constant K
a
1
is always larger than the second dissociation constant
K
a
2
. This is because when the first proton is removed from the acid molecule, it is removed from an electrically
neutral molecule. When the second proton is removed from the acid molecule, it is removed from a negatively
charged species which is energetically less favorable. The effect of the charges on the dissociation of acid
molecule is known as charge effect.

II. Acid-base Equilibria Part 3 Page 3


3. Calculation involving pH, K
a
and K
b


a) Relationship between K
a
and K
b
(pK
a
and pK
b
)

Sometimes the value of K
a
and K
b
can also be expressed in negative log scale known as pK
a
and pK
b
.

pK
a
= -log[K
a
]
pK
b
= - log[K
b
]

For the hydrolysis of a conjugate acid-base pair in water,

HA
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ A
-
(aq)


K
a
=
[H
3
O
+
(aq)
][A
-
(aq)
]
[HA
(aq)
]


A
-
(aq)
+ H
2
O
(l)
d HA
(aq)
+ OH
-
(aq)


K
b
=
[HA
(aq)
][OH
-
(aq)
]
[A
-
(aq)
]


K
a
× K
b
=
[H
3
O
+
(aq)
][A
-
(aq)
]
[HA
(aq)
]
×
[HA
(aq)
][OH
-
(aq)
]
[A
-
(aq)
]
= [H
3
O
+
(aq)
][OH
-
(aq)
] = K
w


K
a
× K
b
= K
w
= 1 × 10
-14
mol dm
-3


OR

-log (K
a
× K
b
) = - log K
w


-log K
a
- log K
b
= - log K
w


pK
a
+ pK
b
=
p
K
w
= 14


b) Relationship between pH, pOH and pK
w


K
w
= [H
3
O
+
(aq)
][OH
-
(aq)
] = 1 × 10
-14
mol dm
-3


-log K
w
= -log ([H
3
O
+
(aq)
][OH
-
(aq)
])

-log K
w
= -log [H
3
O
+
(aq)
] - log [OH
-
(aq)
]

pK
w
= pH + pOH = 14


II. Acid-base Equilibria Part 3 Page 4


c) Some basic assumptions

Depending on whether the small quantity is omitted, there may be two possible answers for a single question.


Calculate the pH of 0.100 M CH
3
COOH
(aq)
. K
a
of CH
3
COOH
(aq)
is 1.70 × 10
-5
mol dm
-3
.


1. The equation is solved accurately

CH
3
COOH
(aq)
d CH
3
COO
-
(aq)
+ H
+
(aq)

concentration at equilibrium (M) 0.100 - x x x

K
a
=
[CH
3
COO
-
(aq)
][H
3
O
+
(aq)
]
[CH
3
COOH
(aq)
]
=
x · x
0.100 - x
mol dm
-3
= 1.70 × 10
-5
mol dm
-3


x = 1.29 × 10
-3
or -1.31 × 10
-3
(rejected)

pH = - log x = - log (1.29 × 10
-3
) = 2.89



2. The equation is solved with the small quantity omitted.

CH
3
COOH
(aq)
d CH
3
COO
-
(aq)
+ H
+
(aq)

concentration at equilibrium (M) 0.100 - x x x

K
a
=
[CH
3
COO
-
(aq)
][H
3
O
+
(aq)
]
[CH
3
COOH
(aq)
]
=
x · x
0.100 - x
mol dm
-3
= 1.70 × 10
-5
mol dm
-3


Since CH
3
COOH
(aq)
is a weak acid, x must be very small comparing with the original concentration (0.1M).
i.e. 0.100 - x ≈ 0.100.

x · x
0.100
= 1.70 × 10
-5


x = 1.30 × 10
-3


pH = - log x = - log (1.30 × 10
-3
) = 2.89

It can be seen that no matter the small quantity is omitted or not, they give similar results. This is because the
degree of dissociation of ethanoic acid is only about 1%.

The dissociation constant of any weak acid with K
a
less than 1 × 10
-4
mol dm
-3
can be neglected in the
expression : (original concentration – x) M. This is applicable to most weak acids.

II. Acid-base Equilibria Part 3 Page 5


3. Basic assumptions


1. Attention must be taken that the small quantity can be omitted only if it is added/subtracted to another number,
but not multiplied/divided to another number.

If x is very small, 0.1 - x ≈ 0.1 but 0.1 · x ≠ 0.1


2. All salts are strong electrolyte and completely ionize in water, only very small percentage is hydrolyzed.

e.g. When NH
4
Cl
(s)
is dissolved in water

NH
4
Cl
(s)

water
 →  NH
4
+
(aq)
+ Cl
-
(aq)


NH
4
+
(aq)
+ H
2
O
(l)
d NH
3(aq)
+ H
3
O
+
(aq)


[NH
4
+
(aq)
] >> [NH
3(aq)
]

The amount of NH
4
+
(aq)
hydrolyzed is considered negligible comparing with the amount of NH
4
+
(aq)
from the
ionization of salt (a strong electrolyte).


3. In alkaline medium, weak acid will be neutralized.

CH
3
COOH
(aq)
+ OH
-
(aq)
→ CH
3
COO
-
(aq)
+ H
2
O
(l)


And because the solution is alkaline, hydrolysis of CH
3
COO
-
(aq)
is very minimal.

CH
3
COO
-
(aq)
+ H
2
O
(l)
d CH
3
COOH
(aq)
+ OH
-
(aq)


[CH
3
COO
-
(aq)
] >> [CH
3
COOH
(aq)
]


Similarly, in acidic medium, weak alkali will also be neutralized.

H
3
O
+
(aq)
+ NH
3(aq)
→ NH
4
+
(aq)
+ H
2
O
(l)


Hydrolysis of the salt is very minimal in acidic medium

NH
4
+
(aq)
+ H
2
O
(l)
d NH
3(aq)
+ H
3
O
+
(aq)


[NH
4
+
(aq)
] >> [NH
3(aq)
]
II. Acid-base Equilibria Part 3 Page 6


4. Example

Some Useful Relationships

K
w
= [H
+
(aq)
][OH
-
(aq)
] = K
a
× K
b
= 1 × 10
-14
mol
2
dm
-6

p
K
w
= pH + pOH

= pK
a
+ pK
b
= 14


Calculate the pH of 0.100 M CH
3
COO
-
Na
+
(aq)
solution. K
a
of CH
3
COOH
(aq)
is 1.70 × 10
-5
mol dm
-3
and K
w
of
water is 1.00 × 10
-14
mol
2
dm
-6
.

Answer 1

CH
3
COO
-
Na
+
(aq)
is a strong electrolyte which completely ionizes in water.

CH
3
COO
-
Na
+
(aq)
→ CH
3
COO
-
(aq)
+ Na
+
(aq)


A very small percentage of CH
3
COO
-
(aq)
hydrolyzes in water and makes the solution alkaline.

CH
3
COO
-
(aq)
+ H
2
O
(l)
d CH
3
COOH
(aq)
+ OH
-
(aq)


Inital concentration (mol dm
-3
) 0.100 0 0
Equilibrium concentration (mol dm
-3
) 0.100 - x x x


K
c
=
[CH
3
COOH
(aq)
][OH
-
(aq)
]
[CH
3
COO
-
(aq)
]
=
x · x
0.100 -x


=
[CH
3
COOH
(aq)
][OH
-
(aq)
]
[CH
3
COO
-
(aq)
]
×
[H
+
(aq)
]
[H
+
(aq)
]
=
[CH
3
COOH
(aq)
]
[CH
3
COO
-
(aq)
][H
+
(aq)
]
× [H
+
(aq)
][OH
-
(aq)
] =
1
K
a
× K
w



x · x
0.100 - x
=
K
w
K
a


Since x << 0.100, therefore 0.100 - x ≈ 0.100


x
2
0.100
=
1.00 × 10
-14
1.70 × 10
-5

x = 7.67 × 10
-6


pOH = - log [OH
-
(aq)
] = - log 7.67 × 10
-6
= 5.12

pH = 14 - pOH = 14 - 5.12 = 8.88

II. Acid-base Equilibria Part 3 Page 7


Anwser 2

Alternatively, the problem can be interpreted as hydrolysis of the base CH
3
COO
-
(aq)
which is the conjugate
base of CH
3
COOH
(aq)
.
CH
3
COO
-
(aq)
+ H
2
O
(l)
d CH
3
COOH
(aq)
+ OH
-
(aq)


Inital concentration (mol dm
-3
) 0.100 0 0
Equilibrium concentration (mol dm
-3
) 0.100 - x x x

Since the dissociation constant of the conjugate acid-base pair is related by the relationship K
w
= K
a
× K
b
.

K
b
=
K
w
K
a
=
1.00 × 10
-14
1.70 × 10
-5 = 5.88 × 10
-10


5.88 × 10
-10
=
[CH
3
COOH
(aq)
][OH
-
(aq)
]
[CH
3
COO
-
(aq)
]
=
x · x
0.100 - x


If the equation is solved exactly, x = 7.67 × 10
-6
or - 7.67 × 10
-6
(rejected)

pOH = - log [OH
-
(aq)
] = - log 7.67 × 10
-6
= 5.12

pH = 14 - pOH = 14 - 5.12 = 8.88


4. Experimental determination of K
a

By half-neutralization


By other methods

Glossary
conductivity dissociation constant acidity constant K
a
basicity constant K
b
polybasic acid
charge effect pH pOH pK
a
pK
b
K
w
pK
w
hydrolysis of salt

Past Paper
Question
91 1A 3 b ii
92 2A 3 c ii
93 1A 1 e
94 1A 1 f ii 94 2A 3 c i
95 2A 2 c i ii iii
96 2A 1 c i
97 1A 2 b

91 1A 3 b ii
3b Write equation(s) to describe the reaction of
ii NaHCO
3(s)
with water. 1
NaHCO
3(s)
→ Na
+
(aq)
+ HCO
3
-
(aq)

HCO
3
-
(aq)
+ H
2
O
(l)
d H
2
CO
3(aq)
+ OH
-
(aq)
1 mark

C ii Most knew the hydrolysis of HCO
3
-
(aq)
to form H
2
CO
3(aq)
and OH
-
(aq)
.

II. Acid-base Equilibria Part 3 Page 8
92 2A 3 c ii
3c ii 40.0 cm
3
of an aqueous solution of a weak acid, HA
(aq)
, was titrated with a strong base, MOH
(aq)
, at 298K. The
initial pH, before the addition of base, was 2.70. At the equivalence point of the titration, the pH was 8.90.
Calculate
(I) the initial concentration of the acid.
(II) the volume of the base added to reach the equivalence point.
(III) the concentration of the base.
(The dissociation constant of the weak acid and the ionic product of water at 298K are respectively
K
a
= 1.8 × 10
-5
mol dm
-3
K
w
= 1.0 × 10
-14
mol
2
dm
-6
)
5
(I) pH = 2.70 ⇒ -log[H
+
] = 2.70 ⇒ [H
+
] = 1.995 × 10
-3

Let a be the concentration of the weak acid
HA d H
+
+ A
-

a - x x x
K
H A
HA
x x
a x
a
= =


= ×
+ −

[ ][ ]
[ ]
. 18 10
5

Since HA is a weak acid a - x ≈ a
∴ Concentration of weak acid = a = 0.2212M 2 marks
(II) Let V be the volume (in cm
3
) of MOH added.
The total volume of the solution at the equivalence point = 40.0 + V (cm
3
)
Total no. of mole of HA present =
40 0 2212
1000
0 008847
×
=
.
. mole
At equivalence point, the amount of acid is the same as the amount of base. Thus, a pure salt solution is
formed. It was because of hydrolysis, the solution is basic.
A
-
+ H
2
O d HA + OH
-

i.e. the [HA] = [OH
-
] at equivalence point
Since pH = 8.90 at equivalence point ⇒ [H
+
] = 1.2589 × 10
-9

and [HA] = [OH
-
] =
10
[H ]

-14
+
=
10
12589 10
14
9


× .
= 7.943 × 10
-6

Also the amount of A
-
at equivalence point can be assumed to be equal to the amount of HA in the original
solution because HA is a weak acid and the solution is alkaline.
Therefore, HA d H
+
+ A
-

at equivalence point, 7.943 × 10
-6
1.2589 × 10
-9

0.008847
(40.0 + V) / 1000

K
a
=
[H ][A ]
[HA]
+ -
= 1.8 × 10
-5
=
1.2589 10
0.008847
(40.0 V) / 1000
7.943 10
9
6
× ×
+
×




1.8 × 10
-5
=
12589 10
7943 10
9
6
.
.
×
×


×
0.008847
(40.0 + V)
× 1000
(40.0 + V) = 77.89 cm
3

or V = 37.89 cm
3
2 marks
(III) Concentration of MOH =
0.008847
37.89
× 1000 = 0.2335 M 1 mark
(Comment : Wrong no. of significant figures in the calculation)

C ii Few candidates obtained all three answers correctly, but marks were awarded for all intermediate steps.

II. Acid-base Equilibria Part 3 Page 9
93 1A 1 e
1e A solution is prepared by dissolving potassium hydrogencarbonate in water at 298 K.
Write chemical equations for four equilibrium reactions, each involving the hydrogencarbonate ions, that occur in
the solution and calculate the value of the equilibrium constant for each reaction.
Give that at 298 K:
K
1
= 4.3 × 10
-7
moldm
-3
; K
2
= 4.8 × 10
-11
moldm
-3
for H
2
CO
3

K
w
= 1.0 × 10
-14
mol
2
dm
-6
for H
2
O
5
HCO
3
-
(aq)
d H
+
(aq)
+ CO
3
2-
(aq)
K
2
= 4.8 × 10
-11
moldm
-3

HCO
3
-
(aq)
+ H
2
O
(l)
d H
2
CO
3(aq)
+ OH
-
(aq)
K =
K
w
K
1
=2.33 × 10
-8
moldm
-3

HCO
3
-
(aq)
+ H
+
(aq)
d H
2
CO
3(aq)

1
K
1
= 2.33 × 10
6
mol
-1
dm
3

HCO
3
-
(aq)
+ HCO
3
-
(aq)
d CO
3
2-
(aq)
+ H
2
CO
3(aq)
K =
K
2
K
1
= 1.12 × 10
-4

HCO
3
-
(aq)
+ OH
-
(aq)
d CO
3
2-
(aq)
+ H
2
O
(l)
K =
K
2
K
w
= 4.8 × 10
3
mol
-1
dm
3

4 marks(½ for equation, ½ for value) for any 4 of the above equilibria
1 mark for correct dimension of equilibrium constants

C Most candidates could get the two equilibria involving HCO
3
-
and H
+
, but failed to realize the two equilibria
involving HCO
3
-
and OH
-
indicating that the candidates were not familiar with the interplay between K
a
and K
b
of
the respective conjugate acid and conjugate base.


94 1A 1 f ii
1f ii For the following equilibrium at 298 K, the equilibrium constant K
c
= 2.84 × 10
-22
(mol dm
-3
)
5
.
Ag
3
PO
4(s)
+ H
2
O
(l)
d 3Ag
+
(aq)
+ HPO
4
2-
(aq)
+ OH
-
(aq)

Calculate the solubility, in mol dm
-3
, of silver phosphate(V) in 0.10 M disodium hydrogenphosphate(V) solution
at pH 10.
Given : Ionic product of water at 298 K = 1.0 × 10
-14
(mol dm
-3
)
2

(Assume the extent of dissociation of HPO
4
2-
ions at pH 10 is negligible.
3
At pH = 10
[OH
-
(aq)
] = 10
-4
moldm
-3

[HPO
4
2-
(aq)
] = 10
-1
moldm
-3

K
c
= [Ag
+
(aq)
]
3
[HPO
4
2-
(aq)
][OH
-
(aq)
] = 2.84 × 10
-22

∴ [Ag
+
(aq)
]
3
= 2.84 × 10
-17

[Ag
+
(aq)
] = 3.05 × 10
-6
moldm
-3

Q 1 mole of Ag
3
PO
4
produces 3 moles of Ag
+
(aq)
ions.
∴ Solubility of Ag
3
PO
4
= 1.017 × 10
-6
moldm
-3
3 marks


94 2A 3 c i
3c Given:
K
a
for CH
3
(CH
2
)
2
COOH = 1.5 × 10
-5
moldm
-3
at 298K
Calculate the pH of

i an aqueous solution of 0.10M CH
3
(CH
2
)
2
COOH; 2

K
a
=
[H
+
][PrCOO
-
]
[PrCOOH]

Assumming [H
+
] = [PrCOO
-
], [PrCOO
-
] = 0.1 1 mark
1.5 × 10
-5
=
[H
+
]
2
0.1

[H
+
] = 1.225 × 10
-3
M
pH = 2.91 1 mark


II. Acid-base Equilibria Part 3 Page 10
95 2A 2 c i ii iii
2c The following reversible reaction occurs in an aqueous solution of ammonium ethanoate :
CH
3
COO
-
(aq)
+ NH
4
+
(aq)
d CH
3
COOH
(aq)
+ NH
3(aq)
(I)

i Write an expression for the dissociation constant, K
a
, of ammonium ion. 1
NH
4
+
d NH
3
+ H
+

K
a
=
[NH
3
][H
+
]
[NH
4
+
]
1 mark

ii Calculate the equilibrium constant of reaction (I) at 298 K.
(At 298 K, the dissociation constants of ethanoic acid and ammonium ion are 1.76 × 10
-5
mol dm
-3
and 5.59 × 10
-
10
mol dm
-3
respectively.)
2
NH
4
+
+ CH
3
COO
-
d NH
3
+ CH
3
COOH
K =
[NH
3
][CH
3
COOH]
[NH
4
+
][CH
3
COO
-
]
1 mark
=
K
a
(NH
4
+
)
K
a
(CH
3
COOH)
=
5.59 × 10
-10
1.76 × 10
-5 = 3.18 × 10
-5
1 mark

iii For a 0.10 M solution of ammonium ethanoate at 298 K,
calculate
(1) the concentration of ammonia, and
(2) the pH of the solution.
4
(1)
Let x = [NH
3
] = [CH
3
COOH]
[NH
4
+
] = [CH
3
COO
-
] = 0.100 - x 1 mark
K =
x
2
(0.100 - x)
2 = 3.18 × 10
-5

x = 5.60 × 10
-4
M 1 mark

(2)
Let y = [H
+
]
K
a
(CH
3
COOH) =
y (100 - x)
x

y = 9.96 × 10
-8
M 1 mark
pH = -log [H
+
] = 7.00 1 mark
OR
K
a
(NH
4
+
) =
y (x)
(0.100 - 5.60 × 10
-4
)

5.59 × 10
-10
=
y (5.60 × 10
-4
)
(0.100 - 5.60 × 10
-4
)

y = 9.93 × 10
-8
M 1 mark
pH = 7.00 1 mark

C The performance of candidates in this question was poor, indicating that they were not able to apply what they had
learnt to a slightly varied situation.


96 2A 1 c i
1c i At 298 K the pH of 0.050 M CH
3
CH
2
COOH is 3.10. Calculate the K
a
of CH
3
CH
2
COOH at 298 K. 2
CH
3
CH
2
COOH d CH
3
CH
2
COO
-
+ H
+

K
a
=
[CH
3
CH
2
COO
-
][H
+
]
[CH
3
CH
2
COOH]
½ mark
Assuming [CH
3
CH
2
COO
-
] = [H
+
] ½ mark

K
a
=
(10
-3.10
)
2
(0.05 - 10
-3.10
)

= 1.26 × 10
-5
mol dm
-3
(1.25 – 1.30 × 10
-5
mol dm
-3
) 1 mark
(Deduct ½ mark for no / wrong unit)


97 1A 2 b
2b Account for the difference in K
a
values given in the following equilibrium reactions:
H
2
SO
4(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ HSO
4
-
(aq)
K
a
= 7.94 × 10
2
mol dm
-3

HSO
4
-
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ SO
4
2-
(aq)
K
a
= 0.10 mol dm
-3



II. Acid-base Equilibria Part 4 Page 1
Topic II. Acid-base Equilibria Part 4

Reference
Reading

6.2.5

Assignment
Reading

Advanced Practical Chemistry, John Murray (Publisher) Ltd., 65–67
A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 271–272
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 374–377
Chemistry in Context (5th ed.), Thomas Nelson and Sons Ltd., 334–337

Syllabus
Buffer

Notes
E. Buffer

Buffer is a solution which resists to pH change upon addition of small amount of acid or alkali. Blood is an
example of buffer solution, which has a constant pH of about 7.4.


1. Principle of buffer action

Since buffer is capable to absorbs both H
+
(aq)
and OH
-
(aq)
, it must be a mixture of an acid and a base. However,
strong acid and strong base cannot coexist, they neutralize each other. Buffer must be a mixture of a conjugate
acid-base pair of a weak acid or weak base.

e.g. A mixture of CH
3
COOH
(aq)
(acid) and CH
3
COO
-
(aq)
(conjugate base), or
A mixture of NH
3(aq)
(base) and NH
4
+
(aq)
(conjugate acid)


For the buffer consists of CH
3
COOH
(aq)
and CH
3
COO
-
Na
+
(aq).

This involves the equilibrium of CH
3
COOH
(aq)
d CH
3
COO
-
(aq)
+ H
+
(aq)


Upon addition of H
+
(aq)
, H
+
(aq)
will be removed by the base CH
3
COO
-
(aq)
.
CH
3
COO
-
(aq)
+ H
+
(aq)
→ CH
3
COOH
(aq)


Upon addition of OH
-
(aq)
, OH
-
(aq)
will be removed by the acid CH
3
COOH
(aq)
.
CH
3
COOH
(aq)
+ OH
-
(aq)
→ CH
3
COO
-
(aq)
+ H
2
O
(l)


Therefore, the pH of the solution can be maintained.

II. Acid-base Equilibria Part 4 Page 2


a) pH of an acidic buffer

For a buffer consists of an acid and its conjugate base (e.g. CH
3
COOH
(aq)
and CH
3
COO
-
Na
+
(aq)
),

CH
3
COOH
(aq)
d CH
3
COO
-
(aq)
+ H
+
(aq)


K
a
=
[CH
3
COO
-
(aq)
][H
+
(aq)
]
[CH
3
COOH
(aq)
]


[H
+
(aq)
] =
K
a
[CH
3
COOH
(aq)
]
[CH
3
COO
-
(aq)
]


pH = -log K
a
- log
[CH
3
COOH
(aq)
]
[CH
3
COO
-
(aq)
]


pH = pK
a
- log
[acid]
[salt]


In a buffer solution, acid and its salt share the same volume

∴ pH = pK
a
- log (
no. of mole of acid / V
no. of mole of salt / V
) = pK
a
- log
no. of mole of acid
no. of mole of salt


The pH is depending on the nature of the acid i.e. pK
a
and the ratio of concentrations of the acid and its salt.
Furthermore, the more concentrate the acid and its salt, the higher will be the buffering capacity of the solution
because it will be able to absorb more base or acid.


b) pH of an alkaline buffer

For an buffer solution involving a weak base and its conjugate acid (e.g. NH
3(aq)
and NH
4
+
(aq)
)

NH
3(aq)
+ H
2
O
(l)
d NH
4
+
(aq)
+ OH
-
(aq)



K
b
=
[NH
4
+
(aq)
][OH
-
(aq)
]
[NH
3(aq)
]


[OH
-
(aq)
] =
K
b
[NH
3(aq)
]
[NH
4
+
(aq)
]


pOH = pK
b
- log
[NH
3(aq)
]
[NH
4
+
(aq)
]


pOH = pK
b
- log
[base]
[salt]


The base and salt share the same solution, therefore,

pOH = pK
b
- log
no. of mole of base
no. of mole of salt



Since pK
w
= pH + pOH = 14, pH = pK
w
- pOH

pH = pK
w
- ( pK
b
- log
[base]
[salt]
) = 14 - pK
b
+ log
[base]
[salt]
)

II. Acid-base Equilibria Part 4 Page 3


2. Calculation of buffer solution

Important relationships

pH = pK
a
- log
[acid]
[salt]
OR pH = pK
a
- log
no. of mole of acid
no. of mole of salt


pOH = pK
b
- log
[base]
[salt]
OR pOH = pK
b
- log
no. of mole of base
no. of mole of salt



pK
w
= pH + pOH = 14


a) pH of buffer solution

Calculate the pH of the buffer solution consists of 0.100 M NH
3(aq)
and 0.0500 M NH
4
+
(aq)
respectively. K
b
of
NH
3(aq)
1.58 × 10
-5
mol dm
-3
.

NH
3(aq)
+ H
2
O
(l)
d NH
4
+
(aq)
+ OH
-
(aq)

Initial concentration (mol dm
-3
) 0.100 0.0500 0
Equilibrium concentration (mol dm
-3
) 0.100 - x 0.0500 + x x

Like the example mentioned in the last unit, the equation can be solved accurately or approximately.

A. The equation is solved accurately.

K
b
=
[NH
4
+
(aq)
][OH
-
(aq)
]
[NH
3(aq)
]
=
(0.0500 + x) x
0.100 - x
= 1.58 × 10
-5


x
2
+ 0.0500 x - 1.58 × 10
-6
= 0

x = 3.16 × 10
-5
or - 0.0500 (rejected)

pOH = - log x = - log (3.16 × 10
-5
) = 4.50

pH = pK
w
- pOH = 14 - 4.50 = 9.50

B. The equation is solved with the approximation applied.

It can be assumed that the
1. hydrolysis of ammonia is very minimal in the presence of NH
4
+
.
∴ [NH
3(aq)
] = (0.100 - x) M ≈ 0.100 M

2. hydrolysis of ammonium ion is also very minimal in the presence of NH
3(aq)
.
[NH
4
+
(aq)
] = (0.0500 + x) M ≈ 0.0500 M

K
b
=
[NH
4
+
(aq)
][OH
-
(aq)
]
[NH
3(aq)
]
=
0.0500 · x
0.100
= 1.58 × 10
-5


x = 3.16 × 10
-5


pOH = - log x = - log (3.16 × 10
-5
) = 4.50

pH = pK
w
- pOH = 14 - 4.50 = 9.50


II. Acid-base Equilibria Part 4 Page 4


C. Solving by applying the equation with approximations applied.

pOH = pK
b
- log
[NH
3(aq)
]
[NH
4
+
(aq)
]


[NH
3(aq)
] = (0.100 - x) M ≈ 0.100 M
[NH
4
+
(aq)
] = (0.0500 + x) M ≈ 0.0500 M

pOH = -log (1.58 × 10
-5
) - log
0.100
0.0500
= 4.50

pH = pK
w
- pOH = 14 - 4.50 = 9.50

Practically, the equation pOH = pK
b
- log
[NH
3(aq)
]
[NH
4
+
(aq)
]
can only be used with the approximations applied. This is
because a quadratic equation cannot be set up without considering the expression of K
b
.

No matter which method is used, they all give the same result (pH = 9.50). This means that the approximations
are valid.

N.B. In the following examples, approximation is used whenever applicable.


b) Effect of addition of acid / alkali into a non-buffered solution

1. Calculate the pH of a 0.200 M CH
3
COOH
(aq)
solution. K
a
of CH
3
COOH
(aq)
is 1.70 × 10
-5
mol dm
-3
.

CH
3
COOH
(aq)
d CH
3
COO
-
(aq)
+ H
+
(aq)

At equilibrium 0.200 - x ≈ 0.200 x x

x · x
0.200
= 1.70 × 10
-5
x = 1.84 × 10
-3


pH = - log [H
+
(aq)
] = - log (1.84 × 10
-3
) = 2.74

2. Calculate the pH of the solution if 0.0500 mole of solid NaOH
(s)
is added into 600 cm
3
of 0.200 M
CH
3
COOH
(aq)
.

No. of mole of CH
3
COOH
(aq)
in 600 cm
3
of 0.200 M = 0.200 mol dm
-3
× 0.600 dm
3
= 0.120 mol

NaOH is a strong alkali which will neutralize 0.0500 mole of CH
3
COOH
(aq)
.

In the equilibrium mixture,
no. of mole of CH
3
COOH
(aq)
= (0.120 - 0.0500) mol = 0.070 mol
no. of mole of CH
3
COO
-
(aq)
= no. of mole of CH
3
COOH
(aq)
neutralized = 0.0500 mol

pH = pK
a
- log
no. of mole of acid
no. of mole of salt
= - log (1.70 × 10
-5
) - log
0.070
0.050
= 4.6

3. Calculate the pH of the solution if 0.0500 mole of HCl
(g)
is dissolved in 600 cm
3
of 0.200 M CH
3
COOH
(aq)
.

Since HCl
(aq)
is a strong acid, the solution will become very acidic. In acidic medium, the ionization of
CH
3
COOH
(aq)
can be neglected comparing with the ionization from HCl
(aq)
.

The effect of change in volume can be neglected when HCl
(g)
is being dissolved.

[H
+
(aq)
] = [HCl
(aq)
] =
0.0500 mol
0.600 dm
-3 = 0.0830 mol dm
-3


pH = - log 0.0830 = 1.08
II. Acid-base Equilibria Part 4 Page 5


c) Effect of addition of acid / alkali into a buffer solution

1. Calculate the pH of a buffer solution with 0.300 M of CH
2
ClCO
2
H
(aq)
and 0.200 M of CH
2
ClCO
2
-
Na
+
(aq)

respectively. K
a
of CH
2
ClCO
2
H
(aq)
is 1.21 × 10
-3
mol dm
-3
.

pH = pK
a
- log
[acid]
[salt]
= - log (1.21 × 10
-3
) - log
0.300
0.200
= 2.74


2. Calculate the pH of the solution if 0.0500 mole of solid NaOH
(s)
is added into 600 cm
3
of the buffer.

no. of mole of CH
2
ClCOOH
(aq)
in 600 cm
3
of the buffer = 0.300 M × 0.600 dm
3
= 0.180 mol
no. of mole of CH
2
COO
-
(aq)
in 600 cm
3
of the buffer = 0.200 M × 0.600 dm
3
= 0.120 mol

When 0.0500 mole of NaOH
(s)
is added, 0.0500 mole of CH
2
ClCO
2
H
(aq)
will be neutralized and 0.0500 mole
of CH
2
ClCOO
-
(aq)
will be produced.

In the equilibrium mixture,
no. of mole of CH
2
ClCOOH
(aq)
= (0.180 - 0.0500) mol = 0.130 mol
no. of mole of CH
2
COO
-
(aq)
= (0.120 + 0.0500) mol = 0.170 mol

pH = pK
a
- log
no. of mole of acid
no. of mole of salt
= - log (1.21 × 10
-3
) - log
0.130
0.170
= 3.03


3. Calculate the pH of the solution if 0.0500 mole of HCl
(g)
is dissolved in 600 cm
3
of the buffer.

no. of mole of CH
2
ClCOOH
(aq)
in 600 cm
3
of the buffer = 0.300 M × 0.600 dm
3
= 0.180 mol
no. of mole of CH
2
ClCOO
-
(aq)
in 600 cm
3
of the buffer = 0.200 M × 0.600 dm
3
= 0.120 mol

CH
2
ClCOOH
(aq)
d CH
2
ClCOO
-
(aq)
+ H
+
(aq)


When 0.0500 mole of HCl
(g)
is dissolved, 0.0500 mole of CH
2
ClCOOH
(aq)
will be produced and 0.0500 mole
of CH
2
ClCOO
-
(aq)
will be consumed.

In the equilibrium mixture,
no. of mole of CH
2
ClCOOH
(aq)
= (0.180 + 0.0500) mol = 0.230 mol
no. of mole of CH
2
COO
-
(aq)
= (0.120 - 0.0500) mol = 0.070 mol

pH = pK
a
- log
no. of mole of acid
no. of mole of salt
= - log (1.21 × 10
-3
) - log
0.230
0.070
= 2.40


d) Comparison of the action of acid and alkali

Original pH Alkali added Acid added
Non-buffered Acid 2.74 4.6 1.08
Buffer solution 2.74 3.03 2.40

Comparatively, the pH of a buffer solution is more resistant to addition of alkali or acid.

For a non-buffered acid, it contains no base to absorb the extra H
+
(aq)
ions if acid is added. Furthermore, with
the acid alone, addition of alkali will cause a big change in
[acid]
[salt]
. This causes a relatively big change in pH.
i.e. pH = pK
a
- log
[acid]
[salt]



II. Acid-base Equilibria Part 4 Page 6


3. Preparation of buffer solution

Usually, a buffer solution is prepared by mixing a weak acid / base with its salt. Or it can be prepared by half-
way titration.

For example, if 1dm
3
of 0.5 M CH
3
COOH
(aq)
requires 0.5 mole of NaOH
(aq)
for complete neutralization. 0.25
mole of NaOH
(aq)
can be added so that only half of the CH
3
COOH
(aq)
will be neutralized.

CH
3
COOH
(aq)
+ OH
-
(aq)
d CH
3
COO
-
(aq)
+ H
2
O
(l)

Initial amount ≈ 0.5 mole ≈ 0.25 mole ≈ 0 mole
Final amount ≈ 0.25 mole ≈ 0 mole ≈ 0.25 mole

Since pH = pK
a
- log
no. of mole of acid
no. of mole of salt
= pK
a
- log 1 = pK
a


This method is used to prepared a buffer solution with the pH equals pK
a
of the acid. For any pH not the same
as pKa, the ratio of no. of mole of acid to no. of mole of salt can be adjusted to prepare a solution of desired
pH.

Glossary
buffer hydrolysis half-way titration

Past Paper
Question
91 2A 2 c i ii
94 2A 3 c ii iii
96 2A 1 c i ii iii
97 2A 4 c ii
98 2A 1 a i ii
99 2A 4 c ii

91 2A 2 c i ii
2c A weak base MOH has an ionization constant K
b
= 2.0 × 10
-5
mol dm
-3
, where K
b
= [M
+
][OH
-
]/[MOH].
Solution S is made up of 0.10 mol of MOH in 1.0 dm
3
, and a second solution T has 0.10 mol of MOH and 0.50
mol of MCl in 1.0 dm
3
.

i Calculate the pH of solutions S and T. 4
MOH d M
+
+ OH
-

Solution S:
Since MOH d M
+
+ OH
-

initial 0.1 0 0
at eqm. 0.1 - x x x
∴ K
b
= 2 × 10
-5
=
x
2
0.1 - x
, assuming (0.1 -x) ≈ 0.1
∴ x = 2 × 10
-6
= 1.414 × 10
-3
M 1 mark
pOH = -log(1.44 × 10
-3
) = 2.85
pH = 14 - 2.85 = 11.15 1 mark
Solution T:
Since MOH d M
+
+ OH
-

initial 0.1 0.5 0
at eqm. 0.1 - x 0.5 + x x
x × (0.5 + x)
0.1 - x
= 2 × 10
-5
with 0.5 + x ≈ 0.5 and 0.1 - x ≈ 0.1
x = 2 × 10
-5
×
0.1
0.5
= 4 × 10
-6
M 1 mark
-log (4 × 10
-6
) = 5.40
pH = 14 - 5.40 = 8.60 1 mark

II. Acid-base Equilibria Part 4 Page 7

ii 0.01 mol of a strong acid HX is added separately to the solutions S and T. The new pH value for solution S is
10.26; calculate that for solution T. What conclusion can you draw from this result?
(K
w
= 1.0 × 10
-14
mol
2
dm
-6
)
4
Solution T:
Since MOH d M
+
+ OH
-

Before addition of acid and hydrolysis 0.1 0.5
Upon addition of acid 0.1 - 0.01 0.5 + 0.01 0
Upon hydrolysis at eqm. 0.09 - x 0.51 + x x 1 mark
x × (0.51 + x)
0.09 - x
= 2 × 10
-5
with 0.51 + x ≈ 0.51 and 0.09 - x ≈ 0.09
x = 2 ×
9
51
× 10
-5
= 3.53 × 10
-6
1 mark
-log (3.53 × 10
-4
) = 5.45
pH = 8.55 1 mark
Solution T can resist the change in pH to a greater extent than solution S, it is generally known as a buffer.
1 mark

C i Most candidates were not able to work out the final pH of solution T.

94 2A 3 c ii iii
3c Given:
K
a
for CH
3
(CH
2
)
2
COOH = 1.5 × 10
-5
moldm
-3
at 298K
Calculate the pH of

ii an aqueous solution of 0.050M CH
3
(CH
2
)
2
COONa and 0.050M CH
3
(CH
2
)
2
COOH; and 2
Assuming [PrCOOH] = 0.050 M
[PrCOO
-
] = 0.050 M
1.5 × 10
-5
= [H
+
] ×
0.50
0.50
1 mark
[H
+
] = 1.5 × 10
-5
M
pH = 4.82 1 mark

iii 1.0 dm
3
of the solution in (ii) after the addition of 1.0 × 10
-3
mol of solid NaOH. 3
After addition of 1.0 × 10
-3
moles solid NaOH
[PrCOOH] = 0.050 - 1.0 × 10
-3
= 0.049 M
[PrCOO
-
] = 0.050 + 1.0 × 10
-3
= 0.051 M 1 mark
1.5 × 10
-5
=
[H
+
] (0.051)
(0.049)

[H
+
] = 1.44 × 10
-5
M 1 mark
pH = 4.34 1 mark


96 2A 1 c i ii iii
1c i At 298 K the pH of 0.050 M CH
3
CH
2
COOH is 3.10. Calculate the K
a
of CH
3
CH
2
COOH at 298 K. 2
CH
3
CH
2
COOH d CH
3
CH
2
COO
-
+ H
+

K
a
=
[CH
3
CH
2
COO
-
][H
+
]
[CH
3
CH
2
COOH]
½ mark
Assuming [CH
3
CH
2
COO
-
] = [H
+
] ½ mark

K
a
=
(10
-3.10
)
2
(0.05 - 10
-3.10
)

= 1.26 × 10
-5
mol dm
-3
(1.25 – 1.30 × 10
-5
mol dm
-3
) 1 mark
(Deduct ½ mark for no / wrong unit)

ii Calculate the pH at 298 K of a solution which is 0.050 M with respect to CH
3
CH
2
COOH and to CH
3
CH
2
COONa. 2
In the solution,
[CH
3
CH
2
COO
-
] = [CH
3
CH
2
COOH] = 0.05 M
K
a
= [H
+
]
∴ pH = pK
a
1 mark
= 4.90 (4.88 – 4.90) 1 mark

iii 5.0 × 10
-4
mol of solid NaOH were added separately to
(1) 100 cm
3
of 0.050 M CH
3
CH
2
COOH and
(2) 100 cm
3
of the solution in (ii) above.
Assuming that the change in volume upon the addition of NaOH is negligible calculate the pH at 298 K of the
solution in each case. Comment on the difference in the pH change of the two solutions.
5
(1) For 100 cm
3
of 0.05 M CH
3
CH
2
COOH
[CH
3
CH
2
COO
-
] = 5.0 × 10
-3
M ½ mark

II. Acid-base Equilibria Part 4 Page 8
[CH
3
CH
2
COOH] = 4.5 × 10
-2
M ½ mark
K
a
=
[H
+
] (5.0 × 10
-3
)
4.5 × 10
-2
[H
+
] = 1.13 × 10
-4
mol dm
-3
(1.15 × 10
-4
mol dm
-3
)
pH = 3.95 (3.93 – 3.96) 1 mark

(2) For 100 cm
3
of the solution in (ii),
[CH
3
CH
2
COO
-
] = 5.5 × 10
-2
M ½ mark
[CH
3
CH
2
COOH] = 4.5 × 10
-2
M ½ mark
K
a
=
[H
+
] (5.5 × 10
-2
)
4.5 × 10
-2
[H
+
] = 1.03 × 10
-5
mol dm
-3
(1.05 × 10
-5
mol dm
-3
)
pH = 4.99 (4.97 – 5.00) 1 mark

0.05 M CH
3
CH
2
COOH is not a buffer ∴ pH changes significantly 1 mark
or, the solution in (ii) is a buffer ∴ pH change is very small (1 mark)

97 2A 4 c ii
4c A solution is formed by mixing equal volumes of 0.20 M CH
3
CO
2
H
(aq)
and 0.20 M CH
3
CO
2
Na
(aq)
. 7
ii Calculate the concentration of each chemical species, excluding H
2
O, present in the solution at 298 K.
(K
a
of CH
3
CO
2
H = 1.76 × 10
-5
mol dm
-3
at 298 K)


98 2A 1 a i ii
1a Solution A is 0.15 M lactic acid, and solution B is a mixture of equal volumes of 0.30 M lactic acid and 0.10 M
aqueous sodium hydroxide solution.
Note : (1) Lactic acid is a monprotic acid and its K
a
at 298 K is 1.38 × 10
-4
moldm
-3
.
(2) For (ii) and (iii), you may assume that the volume changes are negligible.
9
i Calculate the pH of A and of B at 298 K.
ii A few drops of dilute hydrochloric acid are added to 50.0 cm
3
of A and B.
Compare the effect of such action on the pH of the two solutions. Explain your answer.


99 2A 4 c ii
4c ii Given the following materials and apparatus, describe a method to determine the dissociation constant, K
a
, of
HCO
2
H.
approximately 0.1 M aqueous HCO
2
H,
approximately 0.1 M aqueous NaOH,
phenolphthalein indicator,
titration apparatus,
and a calibrated pH meter



II. Acid-base Equilibria Part 5 Page 1
Topic II. Acid-base Equilibria Part 5

Reference
Reading

6.2.6–6.2.7


Assignment
Reading

Advanced Practical Chemistry, John Murray (Publisher) Ltd., 68–69
Experiment – Acid-base titration using method of double indicator
A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 264–270
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 371–374
Chemistry in Context (5th ed.), Thomas Nelson and Sons Ltd., 331–334

Syllabus
Indicators
Acid-base titration

Notes
F. Theory of Indicator

Acid-base indicator is a weak acid which has different colour at different pH. Actually, the conjugate acid-
base pair of the acid have different colour.

HIn
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ In
-
(aq)
K
in
=
[H
3
O
(aq)
+
][In
-
(aq)
]
[HIn
(aq)
]

Colour I Colour II

For example, methyl orange is a weak acid. The conjugate acid of methyl orange is red in colour while the
conjugate base of methyl orange is yellow.

Methyl orange (pK
in
of methyl orange = 3.7)
N N S N
H
3
C
H
3
C
O
O
O
-
+
H
3
O
+
N N S N
H
3
C
H
3
C
O
O
OH H
2
O +
Conjugate acid (red) Conjugate base (yellow)

In acidic medium, the concentration of H
+
(aq)
is high and the equilibrium position is lying on the left.
Therefore, it will be red in colour in acidic medium. For a similar reason, it is yellow in colour in alkaline
medium.

Phenolphthalein is also a weak acid. Its conjugate acid is colourless while the conjugate base is red. Because
methyl orange and phenolphthalein have different K
in
, they change colour at different pH.

Phenolphthalein (pK
in
of phenolphthalein = 9.3)
C
C
O
O
OH
HO
C HO
O
-
OH
C
O
O
-
+
3H
2
O
+ 2H
3
O
+
Conjugate acid (colourless) Conjugate base (red)


II. Acid-base Equilibria Part 5 Page 2


However, a naked eye cannot distinguish colours accurately. It cannot notice any difference unless the
intensity of one colour is ten times of another.

For methyl orange, pK
in
= 3.7

HMe
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ Me
-
(aq)
K
in
=
[H
3
O
(aq)
+
][Me
-
(aq)
]
[HMe
(aq)
]


Therefore, it will become red at pH = , i.e.
[acid]
[salt]
= 10

pH = pK
in
- log
[acid]
[salt]
= pK
in
- log 10 = 3.7 - 1 = 2.7

The solution will become yellow at pH = , i.e.
[acid]
[salt]
=
1
10


pH = pK
a
- log
[acid]
[salt]
= pK
in
- log
1
10
= 3.7 + 1 = 4.7

The pH range from 2.7 to 4.7 is called the working range of methyl orange.

N.B. Working range of a pH indicator = pK
in
± 1

Phenolphthalein works in the same way as methyl orange. It has pK
in
9.3, therefore, the working range of
phenolphthalein is from pH 8.3 to 10.3.

Because indicator is actually an acid, only minimal amount of indicator should be added during a titration. So
that the pH of the solution will not be affected.



G. Acid-base titration

Titration is a process for determining the volume of one solution required to react quantitatively with a given
volume of another. One solution is added to the other, a small amount at a time until just sufficient has been
added to complete the reaction. The equivalence point is determined as an end point. Titrations may be carried
out by hand from a burette or automatically.

1. Difference between equivalence point and end point

Equivalence point – the stage in a titration when the reactants and products are present in equivalent
amounts according to the stoichiometry of the reaction.

End point – the stage in a titration when a change (e.g. colour, pH, temp., conductivity changes) is observed
indicating the end of the titration.

The accuracy of a titration is depending on how close the end point (experimental value) is to the equivalence
point (theoretical value).

II. Acid-base Equilibria Part 5 Page 3


2. Titration using pH meter

About the equivalence point of most acid-base titration, the solution shows a great pH change upon addition of
small amount of acid or base. By plotting a graph with the pH of the solution against the volume of titrant
added, the end point can be determined. The graphy is usually called titration curve.



For the titration between a weak acid and a weak base, plotting of a pH graph is not applicable because there is
no abrupt pH change throughout the course. It is hard to decide where is the end point.


II. Acid-base Equilibria Part 5 Page 4


3. Titration using indicator

a) Choosing of indicator

Choosing of indicator has a great impact on the accuracy of titration. A wrongly chosen indicator will cause a
large error. The selection is depending on the shape of the pH curve of titration. The indicator is chosen so that
the abrupt change on the pH curve will fall across the working range of the indicator.

The value of pK
in
should be close to the value of the pH of the solution at the end-point, so that the colour
change occurs as closely as possible to the equivalence point.



In the titration of strong acid versus
strong base, the equivalence point will be
at pH 7 because the salt formed will not
hydrolyse in water.

Although neither methyl orange nor
phenolphthalein changes colour at pH 7,
the colour will change with a volume very
close to the equivalence point.

Therefore, both methyl orange and
phenolphthalein can be used in the
titration between a strong acid and a
strong base.

Conversely, in the titration of weak acid
versus strong base, the equivalence point
will be higher than pH 7, because of
hydrolysis of the salt.

A
-
(aq)
+ H
2
O
(aq)
d HA
(aq)
+ OH
-
(aq)


Furthermore, the vertical portion of the
pH curve will also be shifted to the higher
pH range.

If phenolphthalein is used, the end point
will be very close to the equivalence
point.

However, if methyl orange is used, the
colour will change far before the
equivalence point is reached. And a large
error will be caused.

Therefore, only phenolphthalein can be
used in the titration between a weak acid
and a strong base.


II. Acid-base Equilibria Part 5 Page 5


Litmus is usually not used in titration because the colour change is not as obvious as methyl orange and
phenolphthalein. It is only used in the form of litmus paper where a white background is available.

In a titration of a strong acid and weak base, methyl orange should be used.
In a titration of a weak acid and a strong base, phenolphthalein should be used.
In a titration of a strong acid and a strong base, either methyl orange or phenolphthalein can be used.

pH value
Indicator 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
methyl orange | red |orange| yellow |
phenolphthalein | colourless |pale pink| red |

For the titration between a weak acid and a weak base, no indicator is appropriate because there is no abrupt
pH change throughout the course.

The end point of a titration between a weak acid and a weak base can neither be detected by any indicator nor
a pH meter. The end points are usually determined by thermometric titration or conductimetric titration.




4. Thermometric titration

Since neutralization is exothermic, the temperature of the solution will increase until the equivalence point is
reached. However, the addition of any cold excess titrant into the warm solution will cause a drop in
temperature. According to this principle, by plotting a graph with the temperature versus the volume of the
titrant added, the end point can be determined.


The graph is composed of 2 straight
lines. One representing the exothermic
reaction and another represents the
cooling. The end point is where the two
straight lines intersect each other.


N.B. According to the theory behind
thermometric titration, the
points on the graph should not
be joined together by a smooth
curve.


II. Acid-base Equilibria Part 5 Page 6


5. Conductimetric titration


Depending on the nature of the acid, base and the
salt formed, the conductivity / conductance of the
solution will also change throughout the titration
process.

Conductivity of a solution depends on
i) ionic concentration
ii) mobility of the ions

a) Strong acid vs Strong base

If a strong acid is titrated against a strong base, the
product will be water and the salt.

For example, in the titration between NaOH
(aq)
and
HCl
(aq)
,

NaOH
(aq)
+ HCl
(aq)
→ H
2
O
(l)
+ NaCl
(aq)


At the beginning, the solution contains only H
+
(aq)

and Cl
-
(aq)
. Upon neutralization, a pair of H
+
(aq)
and
OH
-
(aq)
ions is converted to a H
2
O
(l)
molecule.
Consequently H
+
(aq)
in the acid is replaced by
Na
+
(aq)
which has lower conductivity. Therefore, the
conductivity will drop before the end point. Beyond
the end point, addition of a strong base (a strong
electrolyte) increases the ionic concentration, thus
the conductivity. Furthermore, the excess OH
-
(aq)

ions are more conductive.

The end point is determined by extrapolating the
two sessions of the graph with 2 straight lines.






b) Weak acid vs Strong base

At the beginning, the acid solution contains mainly undissociated acid molecules and the conductance is
minimal. The addition of a strong base will convert the molecular acid molecules to ionic salt. Thus, the
conductivity will increase. Beyond the end point, the conductivity will increase even further upon the addition
of excess strong base.

c) Weak acid vs Weak base

However, if the titration is between a weak acid and a weak base

HA
(aq)
+ BOH
(aq)
→ H
2
O
(l)
+ A
-
(aq)
+ B
-
(aq)


Two covalent molecule reacts to form 1 water molecule and 2 ions. The increases in ionic concentration will
cause an increase in conductivity, Beyond the end point, the addition of the weak acid will only dilute the
solution and the conductivity will decreases.

N.B. Sometimes, it is difficult to predict the actual shape of the graph but a sudden change in slope can be
treated as the existence of end point.

Glossary
indicator methyl orange phenolphthalein K
in
naked eye working range titration
equivalence point end point titration curve (pH curve) indicator thermometric titration
conductimetric titration conductivity / conductance ionic concentration extrapolating

II. Acid-base Equilibria Part 5 Page 7

Past Paper
Question
90 1A 3 a
92 2A 3 c i
94 2A 3 b ii
95 1B 4 e i ii
98 2A 1 a iii
99 1A 4 b i ii 99 1A 4 c

90 1A 3 a
3a Explain why phenolphthalein turns pink in a solution of sodium carbonate, but remains colourless in a solution of
sodium hydrogencarbonate.

CO
3
2-
and HCO
3
-
hydrolyse to a different extent. ½ mark
In a solution of Na
2
CO
3
, CO
3
2-
+ H
2
O d HCO
3
-
+ OH
-
½ mark
resulting in a pH sufficiently high ( and [H
+
] sufficiently low)
such that the equilibrium, In(red) + H
+
d InH
+
(colourless) 1 mark
lies to the left and a pink colour is exhibited.
In a solution of NaHCO
3
, whose pH is also above 7, ½ mark
[H
+
] is sufficiently high for the equilibrium to shift to the right.

C Few candidates were able to answer that a solution of Na
2
CO
3
has a higher pH value than that of a solution of
NaHCO
3
because the hydrolysis of CO
3
2-
and HCO
3
-
takes place to a different extent; and that at the higher pH,
phenolphthalein exists in a form which has a resonance structure and the solution becomes pink.


92 2A 3 c i
3c i Explain the difference between the equivalence point and the end point of a titration. 2
Equivalence point is the point in the titration where moles of acid equals moles of base, corresponding to a salt
solution. The end point is the point in a titration where a particular indicator changes colour which occurs at pH
close to the value of pK
a
for the indicator. 2 marks


94 2A 3 b ii
3b Account for each of the following:
ii At 298K, in a solution of pH 7.0, the indicator methyl orange shows its alkaline colour (yellow), while
phenolphthalein shows its acidic colour (colourless).
3
Acid-base indicators are weak acids / bases.
The dissociation of which can be represented by
HIn
(aq)
+ H
2
O
(l)
d H
3
O
+
(aq)
+ In
-
(aq)
1 mark
The colour of an indicator depends on the relative concentrations of the acidic form, HIn and the alkaline form In
-
(aq)
which are of different colours. ½ mark
The dissociation constant K
i
of different acid-base indicators are different, thus they change colour over different
pH range. The pH range of methyl orange is below 7, while that of phenolphthalein is above 7. ∴ at pH 7, methyl
orange shows its alkaline colour, while phenolphthalein shows its acidic colour. 1½ mark

C ii Very few candidates mentioned the fact that an acid-base indicator is a weak acid or weak base. They also failed
to relate the colour of the indicator to its pH range.


95 1B 4 e i ii
4e For each of the volumetric analyses (i) to (iii), state whether an indicator is required. If an indicator is required,
select the appropriate one from those given below:
litmus; methyl orange; phenolphthalein; potassium dichromate(VI) solution; starch solution

i ethanedioic acid titrated with sodium hydroxide 1
phenolphthalein 1 mark
ii sulphuric(VI) acid titrated with aqueous ammonia 1
methyl orange 1 mark

98 2A 1 a iii
1a Solution A is 0.15 M lactic acid, and solution B is a mixture of equal volumes of 0.30 M lactic acid and 0.10 M
aqueous sodium hydroxide solution.
Note : (1) Lactic acid is a monprotic acid and its K
a
at 298 K is 1.38 × 10
-4
moldm
-3
.
(2) For (ii) and (iii), you may assume that the volume changes are negligible.

iii 50.0 cm
3
of A and of B are titrated with a strong base.
Compare the pH of the two solutions at the respective equivalence points of the titrations. Explain your answers.


99 1A 4 b i ii c
4b The graph below shows the variation of pH when 25.0 cm
3
of 0. 10 M HCl
(aq)
is titrated against 0. 10 M NaOH
(aq)
.
II. Acid-base Equilibria Part 5 Page 8

i On the above graph, sketch a curve to represent the variation of pH when 25.0 cm
3
of 0. 10 M CH
3
CO
2
H
(aq)
is
titrated against 0. 10 M NaOH
(aq)
.

ii From the table below, choose an appropriate indicator for the titration in (i). Explain your choice.
Indicator pH range of colour change
bromocresol green 3.8 - 5.4
bromothymol blue 6.0 - 7.6
thymolphthalein 8.3 - 10.6

99 1A 4 c
4c Given an aqueous solution of Na
2
CO
3
and NaHCO
3
, suggest how to determine the concentrations of the two
substances by titrimetric method using indicators.


III. Redox Equilibria Part 1 Page 1
Topic III. Redox Equilibria Part 1

Reference
Reading
6.3.1
A-Level Chemistry Syllabus for Secondary School (1995), Curriculum Development Council, 188–189

Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 74–80
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 21–29
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 186–187

Syllabus

Redox Equilibria
Faraday and mole

Notes
III. Redox Equilibria

Redox equilibrium is similar to Acid-base equilibrium. An acid-base equilibrium can be considered as a
competition of donation and acceptance of proton.

Conjugate base + proton d Conjugate acid
e.g. NH
3(aq)
+ H
+
(aq)
d NH
4
+
(aq)


Upon donation of proton, a conjugated acid will be converted to a conjugate base.


Redox equilibrium can also be considered as a competition of donation and acceptance of electron.

Oxidizing agent + electron d Reducing agent
e.g. Mg
2+
(aq)
+ 2e
-
(aq)
d Mg
(s)


Upon donation of electron, a reducing agent will be converted to an oxidizing agent.



A. Redox reaction

A complete redox reaction consists of two systems of redox equilibria, thus two half ionic equation.
One half ionic equation represents the reduction and another represents oxidation.

Reduction (acceptance of electron) Ag
+
(aq)
+ e
-
(aq)
d Ag
(s)

Oxidation (donation of electron) Cu
(s)
d Cu
2+
(aq)
+ 2e
-


Overall redox reaction 2Ag
+
(aq)
+ Cu
(s)
d 2Ag
(s)
+ Cu
2+
(aq)



1. Balancing of redox reaction

In a balanced equation, the no. of atoms and the no. of charges must be balanced at the two sides of the
equation. Furthermore, in a redox reaction, the no. of electrons accepted by oxidizing agent must be the same
as the no. of electrons donated by reducing agent.

Therefore, a balanced redox reaction can be constructed in two ways

a) By combining balanced half-ionic equation
b) By the change in oxidation no.
III. Redox Equilibria Part 1 Page 2


a) By combining balanced half-ionic equation


(1) Steps of writing Balanced Half ionic equation

1. Write down the reactant and the product
Cr
2
O
7
2-
(aq)
→ Cr
3+
(aq)


2. Mass balance – by adding something already existed.
Since the reaction is usually conducted in water medium, equation may be balanced by
i. Adding H
2
O
(l)
for lack of O
ii. Adding H
+
(aq)
for lack of H (from dissociation of water, H
2
O d H
+
+ OH
-
)
Cr
2
O
7
2-
(aq)
→ 2Cr
3+
(aq)
(Balance the no. of Cr)

Cr
2
O
7
2-
(aq)
→ 2Cr
3+
(aq)
+ 7H
2
O
(l)
(Add H
2
O
(l)
for lack of O)
14H
+
(aq)
+ Cr
2
O
7
2-
(aq)
→ 2Cr
3+
(aq)
+ 7H
2
O
(l)
(Add H
+
(aq)
for lack of H)


3. Charge balance – Add e
-
to balance the charge
14H
+
(aq)
+ Cr
2
O
7
2-
(aq)
→ 2Cr
3+
(aq)
+ 7H
2
O
(l)

(14 × +1) + (-2) = +12 (2 × +3) + (0) = +6
14H
+
(aq)
+ Cr
2
O
7
2-
(aq)
+ 6e
-

→ 2Cr
3+
(aq)
+ 7H
2
O
(l)

(14 × +1) + (-2) + (6 × -1) = +6 (2 × +3) + (0) = +6

4. Check once again
14H
+
(aq)
+ Cr
2
O
7
2-
(aq)
+ 6e
-

→ 2Cr
3+
(aq)
+ 7H
2
O
(l)

Mass: 14H + 2Cr + 7O 2Cr + 14H + 7O
Charge: (14 × +1) + (-2) + (6 × -1) = +6 (2 × +3) + (0) = +6

Note: Balancing of half-ionic equation can only be started with correct reactant and product, which
can only be memorized.


(2) Combining half-ionic equations

In a redox reaction, an oxidizing agent must react with a reducing agent. i.e. Oxidizing agent does not
react with another oxidizing agent.

By combining an oxidation half equation and a reduction half equation, the ionic equation can be
reconstructed. (First of all, the half ionic equations must be balanced.)

For example,

Reduction half ionic equation Ag
+
(aq)
+ e
-
→ Ag
(s)
(Oxidizing agent: Ag
+
(aq)
)
Oxidation half ionic equation Cu
(s)
→ Cu
2+
(aq)
+ 2e
-
(Reducing agent: Cu
(s)
)

Since the no. of e
-
gained by Ag
+
(aq)
must equal the no. of e
-
lost by Cu
(s)
, ∴ 2 Ag
+
are needed for each Cu.


Reduction half ionic equation 2Ag
+
(aq)
+ 2e
-
→ 2Ag
(s)

Oxidation half ionic equation Cu
(s)
→ Cu
2+
(aq)
+ 2e
-

––––––––––––––––––––––––––––––––––––––––
2Ag
+
(aq)
+ 2e
-
+ Cu
(s)
→ 2Ag
(s)
+ Cu
2+
(aq)
+ 2e
-

(left and right must have the same no. of e
-
)

Overall ionic equation 2Ag
+
(aq)
+ Cu
(s)
→ 2Ag
(s)
+ Cu
2+
(aq)

III. Redox Equilibria Part 1 Page 3


b) By the change in oxidation no.

Since O.N. is the difference between the no. of electron and no. of proton associated with an atom, an increase
in O.N. by 1 is equivalent to losing of 1 e-. Similarly, a decrease in O.N. by 1 is equivalent to gaining of 1 e-.

Oxidizing agent MnO
4
-
(aq)
→ Mn
2+
(aq)
Each Mn gains 5 electrons
+7 +2

Reducing agent Fe
2+
(aq)
→ Fe
3+
(aq)
Each Fe loses 1 electron

+2

+3

By the fact that the no. of electron gained by the oxidizing agent must be the same as the no. of electron lost by
the reducing agent, each MnO
4
-
(aq)
must reacts with 5 Fe
2+
(aq)
.

Therefore, the equation will become

MnO
4
-
(aq)
+ 5Fe
2+
(aq)
→ Mn
2+
(aq)
+ 5Fe
3+
(aq)
No. of O is not balanced, so add some
H
2
O
(l)
.

MnO
4
-
(aq)
+ 5Fe
2+
(aq)
→ Mn
2+
(aq)
+ 5Fe
3+
(aq)
+ 4H
2
O
(l)
No. of H is not balanced, so add some
H
+
(aq)
.

MnO
4
-
(aq)
+ 5Fe
2+
(aq)
+ 8H
+
(aq)
→ Mn
2+
(aq)
+ 5Fe
3+
(aq)
+ 4H
2
O
(l)
Check the no. of atoms and charges
again

mass charge mass charge
1 Mn (-1) + 5×(+2) + 8×(+1) 1 Mn (+2) + 5×(+3)
4 O = +17 4 O = +17
5 Fe 5 Fe
8 H 8 H

The equation, MnO
4
-
(aq)
+ 5Fe
2+
(aq)
+ 8H
+
(aq)
→ Mn
2+
(aq)
+ 5Fe
3+
(aq)
+ 4H
2
O
(l)
, is balanced.

This method is particularly useful in answering M.C. question where the completely balanced equation is
usually not required.



2. Faraday and mole

In counting the no. of atom, mole is used as the counting unit and method of counting by weighing is used.

In counting the no. of electron, method of counting charges is used. The amount of charges carried by 1 mole
of electrons is called 1 Faraday of charges (1 F). 1 Faraday of charges is found to be 96500 Coulombs (96500
C).

6.02 × 10
23
electron charges ≡ 1 F of charges ≡ 96500 C

1 electron charge ≡
1
6.02 × 10
23 F ≡
96500
6.02 × 10
23 C

1 electron charge ≡ 1.66 × 10
-24
F ≡ 1.60 × 10
-19
C


By measuring the size of the current and the time taken, the amount of charges flowing through a circuit can
be measured.

Charges (Q) = Current (I) × Time (t)

If the current is measured in ampere (A) and the time is measured in second (s), the unit of charge will be
coulomb (C).

Charges (Q) = Current (I) × Time (t)
1 C = 1 A × 1 s
1 C = 1 As
III. Redox Equilibria Part 1 Page 4


3. Calculation of mass liberated in electrolysis


In the electrolysis of CuSO
4(aq)
using graphite electrodes, Cu
(s)

will deposit on the cathode and O
2(g)
will evolve at the anode.
By measuring the size of current and the time taken of
electrolysis, the amount of Cu
(s)
and O
2(g)
can be calculated.

In the circuit, rheostat and ammeter must be installed to adjust
and measure the current.

For example, if a beaker of CuSO
4(aq)
is electrolyzed at 200 mA
for 20 minutes, what will be the mass of Cu(s) deposited on the
cathode and the volume of oxygen evolved at the anode.

All volume is measured at standard temperature and pressure.
(Given : Relative atomic mass Cu : 63.55; O : 16.00
Molar volume of gas at s.t.p. is 22.4 dm
3
)



At cathode Cu
2+
(aq)
+ 2e
-
→ Cu
(s)

At anode 4OH
-
(aq)
→ O
2(g)
+ 2H
2
O
(l)
+ 4e
-


By the relationship Q = It,
No. of coulombs flowing through the circuit = Current in ampere × time in second
=
200
1000
A × (20 × 60) s
= 240 C
No. of mole of electron flowing through the current =
charges in coulomb
Faraday constant
=
240
96500 C
= 2.49 × 10
-3
mol

Formation of each mole of Cu
(s)
requires 2 moles of electron, therefore,

no. of mole of Cu
(s)
formed =
no. of mole of electron
2
=
2.49 × 10
-3
mol
2
= 1.25 × 10
-3
mol

Mass of Cu
(s)
deposited = no. of mole of Cu
(s)
× molar mass of Cu = 1.25 × 10
-3
mol × 63.55 g mol
-1
= 0.0794
g


Similarly, formation of each mole of O
2(g)
requires losing of 4 mole of electron.

no. of mole of O
2(g)
formed =
no. of mole of electron
4
=
2.49 × 10
-3
mol
4
= 6.23 × 10
-4
mol

Volume of O
2(g)
at s.t.p. = no. of mole of oxygen × molar volume of gas at s.t.p.
= 6.23 × 10
-4
mol × 22.4 dm
3
mol
-1

= 0.0140 dm
3
= 14.0 cm
3


Glossary
redox equilibrium oxidizing agent reducing agent conservation of mass and charge
faraday (F) coulomb (C)

III. Redox Equilibria Part 1 Page 5

Past Paper
Question
91 2A 2 b i ii
92 2A 2 a i
93 1A 1 d i ii 93 2A 3 a i ii
93 2B 6 b
94 1A 1 d e i ii 94 2B 4 e i ii
95 1A 2 b i 95 2B 4 b i ii
97 1A 1 b
99 2A 4 b i ii

91 2A 2 b i ii
2b i CrO
4
2-
ions react with S
2
O
3
2-
ions to form Cr(OH)
4
-
and SO
4
2-
ions in basic medium. Write balanced equations for
each half reaction and for the overall reaction.
3
CrO
4
2-
+ 4H
2
O + 3e
-
→ Cr(OH)
4
-
+ 4OH
-
1 mark
S
2
O
3
2-
+ 10OH
-
→ 2SO
4
2-
+ 5H
2
O + 8e
-
1 mark
overall equation :
8CrO
4
2-
+ 3S
2
O
3
2-
+ 17H
2
O → 8Cr(OH)
4
-
+ 6SO
4
2-
+ 2OH
-
1 mark

ii What volume of 0.50M Na
2
CrO
4
solution is needed to react completely with 40.0 cm
3
of 0.20M Na
2
S
2
O
3
solution
in basic medium?
2
No. of mole of S
2
O
3
2-
= 0.2 × 40 × 10
-3

Since 3 moles of S
2
O
3
2-
≡ 8 moles of CrO
4
2-
1 mark
∴ no. of moles of CrO
4
2-
= 0.2 × 40 ×
8
3
× 10
-3

Volume of Na
2
CrO
4
=
0 2 40
8
3
10
050
3
.
.
× × ×

= 0.04267 dm
3
= 42.67 cm
3
1 mark
(no unit -½) (more than 2 decimal places -½)

C i Some candidates failed to recognize that the given reaction takes place in basic medium.
ii Most candidates were not able to write balanced equations for the half-reactions which take place in basic
medium.


92 2A 2 a i
2a In acid solution, chlorate(V) ions, ClO
3
-
, slowly oxidize chloride ions to chlorine. The following kinetic data are
obtained at 25°C.
[ClO
3
-
]/mol dm
-3
[Cl
-
]/mol dm
-3
[H
+
]/mol dm
-3
Initial rate/mol dm
-3

0.08 0.15 0.20 1.0 × 10
-5

0.08 0.15 0.40 4.0 × 10
-5

0.16 0.15 0.40 8.0 × 10
-5

0.08 0.30 0.20 2.0 × 10
-5


i Write the balanced equation for this reaction. 1
The balanced equation for this reaction
ClO
3
-
+ 5Cl
-
+ 6H
+
→ 3Cl
2
+ 3H
2
O 1 mark

C i Weaker candidates were not able to give the balanced equation.

93 1A 1 d i ii
1d Write balanced equations for:
i the reaction between MnO
2(s)
and PbO
2(s)
in acidic solution to give MnO
4
-
(aq)
and Pb
2+
(aq)
. 1½
2MnO
2(s)
+ 3PbO
2(s)
+ 4H
+
(aq)
d 2MnO
4
-
(aq)
+ 3Pb
2+
(aq)
+ 2H
2
O
(l)
1½ mark
ii the reaction between H
2
O
2(aq)
and Cr(OH)
4
-
(aq)
in alkaline solution to give CrO
4
2-
(aq)
. 1½
3H
2
O
2(aq)
+ 2Cr(OH)
4
-
(aq)
+ 2OH
-
(aq)
d 2CrO
4
2-
(aq)
+ 8H
2
O
(l)
1½ mark
C A surprisingly large number of candidates could not do the balancing of equation for redox reactions which
should be basic work for A-Level candidates.


III. Redox Equilibria Part 1 Page 6
93 2A 3 a i ii
3a i Write balanced half equations for the redox reaction of Cr
n+
and MnO
4
-
in acidic solution. In terms of n, how
many moles of electrons per mole of Cr
n+
, are involved in the oxidation reaction?
Write the balanced overall chemical equation for the above reaction.
5
The half reactions
7H
2
O + 2Cr
n+
→ Cr
2
O
7
2-
+ 14H
+
+ (12 - 2n)e
-
2 marks
MnO
4
-
+ 8H
+
+ 5e
-
→ Mn
2+
+ 4H
2
O 1 mark
No. of moles of e
-
per Cr
n+
is (6 - n) 1 mark
Overall equation:
35H
2
O + 10Cr
n+
+ (12 - 2n)MnO
4
-
+ (12 - 2n)8H
+
→ 5Cr
2
O
7
2-
+ 7OH
-
+ (12 - 2n)Mn
2+
+ (12 -2n)4H
2
O
or
10Cr
n+
+ (12 - 2n)MnO
4
-
+ (26 - 16n)H
+
→ 5Cr
2
O
7
2-
+ (12 - 2n)Mn
2+
+ (13 - 8n)H
2
O 1 mark

ii An acidified solution containing 1.50 × 10
-3
mol of Cr
n+
is titrated with 0.0250 M KMnO
4
solution. The
equivalence point of the reaction is reached after 48.00 cm
3
of KMnO
4
has been added.
Calculate the value of n.
4
No. of moles of Cr
n+
is 0.00150
No. of moles of MnO
4
-
is
48.00 × 0.0250
1000
= 0.00120 1 mark
5 moles of Cr
n+
≡ 4 moles of MnO
4
-
1 mark
10
12 - 2n
=
5
4
1 mark
n = 2 1 mark

C This part was unsatisfactorily answered. Many candidates started with wrong equations so that they were not able
to obtain the correct final answer. The balancing of equations for the redox reactions should be given more
attention.


93 2B 6 b
6b In aqueous solution, 1 mole of iodine reacts with 2 moles of thiosulphate ions, whereas 4 moles of bromine reacts
with 1 mole of thiosulphate ions.
Write balanced ionic equations for the two reactions.
Predict the reaction between chlorine and thiosulphate ions in aqueous solution. Explain your prediction.
5
Equation for the reaction between I
2
and S
2
O
3
2-
is I
2
+ 2S
2
O
3
2-
→ 2I
-
+ S
4
O
6
2-
1 mark
for the reaction between 4Br
2
and S
2
O
3
2-
, 4Br
2
+ S
2
O
3
2-
+ 5H
2
O → 8Br
-
+ 2SO
4
2-
+ 10H
+
2 mark
Chlorine will react similarly as bromine because Cl
2
is a stronger oxidising agent when compared with Br
2
and +6
(in SO
4
2-
) is the maximium oxidation state for S. 2 marks

C Few candidates were able to construct the equation for the reaction of bromine and thiosulphate ions. Some
candidates suggested that chlorine could oxidize thiosulphate ions to peroxodisulphate(VI); or that chlorine was a
stronger reducing agent.


94 1A 1 d e i ii
1d An aqueous solution of titanium (Ti) salt was electrolysed by passing a current of 5.00 A for 2.50 hours. As a
result, 5.60 g of metallic Ti were deposited at the cathode. Deduce the charge on the Ti ion in the solution.
Give : 1 faraday = 96500 Cmol
-1

3
Ti
n+
+ ne
-
→ Ti
i.e. 1 mole of Ti produced requires n moles of e
-

no. of moles of Ti liberated =
5.60
47.90
= 1.169 × 10
-1
1 mark
no. of moles of e
-
passed =
5.00 × 2.50 × 60 × 60
96550
= 4.663 × 10
-1
1 mark
∴ n =
4.663 × 10
-1
1.169 × 10
-1 = 3.989 ≈ 4 1 mark

1e Write a balanced equation for each of the following reactions.
i The reaction between BrO
3
-
(aq)
and Br
-
(aq)
in acidic solutions to give Br
2(aq)
. 1½
BrO
3
-
(aq)
+ 5Br
-
(aq)
+ 6H
+
(aq)
→ 3Br
2(aq)
+ 3H
2
O
(l)
1½ mark
½ mark for completing the equation
1 mark for balancing the equation

ii The reaction between MnO
4
-
(aq)
and SO
2(g)
in alkaline solution to give MnO
2(s)
and SO
4
2-
(aq)
. 1½
2MnO
4
-
(aq)
+ 3SO
2(g)
+ 4OH
-
(aq)
→ 2MnO
2(s)
+ 3SO
4
2-
(aq)
+ 2H
2
O
(l)
1½ mark
½ mark for completing the equation
1 mark for balancing the equation

C Generally well-answered, except that some candidates still put electrons in the overall equation.
III. Redox Equilibria Part 1 Page 7
94 2B 4 e i ii
4e In concentrated HCl, 1 mole of hydrazine H
2
NNH
2
reacts with 1 mole of potassium iodate(V) to give 1 mole of
iodine monochloride ICl with the evolution of a colourless gas.

i Deduce, the oxidation state of nitrogen in the reaction product, and hence suggest what the colourless gas might
be.
2

Q NH
2
NH
2
: IO
3
-
= 1 : 1
In the reduction of IO
3
-
, O.S. of I decreases from +5(IO
3
-
) to +1(ICl)
∴ In the oxidation of NH
2
NH
2
, 4 moles of e
-
should be released from each mole of NH
2
NH
2
. 1 mark
In 1 mole of NH
2
NH
2
, there are 2 moles of N atoms.
∴ O.S. of N in the reaction product is 0. ½ mark
The colourless gas in probably N
2
. ½ mark

ii Write balanced half-equations and a balanced overall equation for the reaction. 3
IO
3
-
+ 5H
+
+ HCl + 4e
-
→ ICl + 3H
2
O 1 mark
NH
2
NH
2
→ N
2
+ 4H
+
+ 4e
-
1 mark
IO
3
-
+ H
+
+ HCl + NH
2
NH
2
→ ICl + N
2
+ 3H
2
O 1 mark
OR
IO
3
-
+ 5H
+
+ HCl + 4e
-
→ ICl + 3H
2
O 1 mark
NH
3
NH
3
2+
→ N
2
+ 6H
+
+ 4e
-
1 mark
IO
3
-
+ HCl + NH
3
NH
3
2+
→ ICl + N
2
+ 3H
2
O + H
+
1 mark

C This question demanded application of knowledge to an unfamiliar situation and was poorly-answered. Only a
few candidates worked out the identity of the colourless gas from the change in oxidation states of nitrogen. Some
candidates gave I
+
, instead of ICl, as the product in the reduction of IO
3
-
.


95 1A 2 b i
2b i What is the essential feature of a "redox reaction" ? 1
“Redox reaction” : a reaction involving the transfer of electron(s) from one reactant to another 1 mark
OR
A reaction involving a change in oxidation state / oxidation no. 1 mark

C i Generally well answered, except that some candidates did not point out the essential feature of a redox reaction.
They just wrote that a redox reaction involves reduction and oxidation.


95 2B 4 b i ii
4b Give the oxidation states of iodine in the two equations below. Balance the equation in each case.
i S
2
O
3
2-

(aq)
+ I
2(aq)
→ S
4
O
6
2-

(aq)
+ I
-
(aq)
2
Oxidation state of I in I
2
= 0 1 mark
Oxidation state of I in I
-
= -1
2S
2
O
3
2-

(aq)
+ I
2(aq)
→ S
4
O
6
2-

(aq)
+ 2I
-
(aq)
1 mark

ii I
-
(aq)
+ IO
3
-
(aq)
+ H
+
(aq)
→ I
2(aq)
+ H
2
O
(l)
2
Oxidation state of I in I
-
= -1 1 mark
Oxidation state of I in IO
3
-
= +5 / V
Oxidation state of I in I
2
= 0
5I
-
(aq)
+ IO
3
-
(aq)
+ 6H
+
(aq)
→ 3I
2(aq)
+ 3H
2
O
(l)
1 mark

C ii Many candidates could not give the correct oxidation state of iodine in IO
3
-
.

97 1A 1 b
1b In a nickel-plating experiment, after passing a current of 5.0 A through an electroplating bath containing a nickel
compound for 5.5 minutes, 0.50 g of metallic nickel was deposited at the cathode. Assuming that the current
efficiency is 100%, deduce the oxidation state of nickel in the compound.
3

99 2A 4 b i ii
4b In an electrolysis experiment, inert electrodes were used and a constant current of 1.00 A was passed for 1800 s
through two electrolytic cells connected in series.

i One of the cells contained an aqueous solution of silver(I) nitrate(V) and 2.02 g of silver was deposited on the
cathode. Deduce the Faraday constant and the charge carried by an electron.

ii The other cell contained an aqueous solution of a gold salt and 1.23 g of gold was deposited on the cathode.
Deduce the oxidation state of gold in the gold salt.
(Assume 100% current efficiency in this experiment.)


III. Redox Equilibria Part 2 Page 1
Topic III. Redox Equilibria Part 2

Reference
Reading
6.3.2
Advanced Practical Chemistry, John Murray (Publisher) Ltd., 108–109
Physical Chemistry (3rd ed.), P.W. Atkins, 259–263

Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 280–281
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 209
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 188, 278–280

Syllabus
Electrochemical cells
Measurement of e.m.f.
Use of salt bridge
Cell diagrams (IUPAC conventions)

Notes
B. Electrochemical cells

If a reducing agent is mixed with an oxidizing agent, the electrons from the reducing agent flow to the
oxidizing agent directly. The chemical energy of the two reagents will be converted to heat energy.

e.g. Zn
(s)
+ Cu
2+
(aq)
→ Zn
2+
(aq)
+ Cu
(s)

strong strong weak weak
reducing oxidizing oxidizing reducing
agent agent agent agent



However, if a reducing agent is connected to an
oxidizing agent through an external circuit and
completed with a salt bridge, the electrons from the
reducing agent will flow through the external
circuit. In this situation, the chemical energy is
converted to electrical energy. And an
electrochemical cell is constructed.

III. Redox Equilibria Part 2 Page 2


1. Measurement of e.m.f.

e.m.f. of a cell is defined as the potential difference across a cell when the circuit is open. That means the
current is zero. If the current is not zero, owing to the internal resistance of a cell, the potential difference
measured will be lower than the e.m.f.

a) Potentiometer


Potentiometer is the best device to measure the e.m.f. of a cell because the current flowing through the cell to
be measured would be exactly zero.


A standard accumulator is used as the reference in the
potentiometer and the circuit is connected as the
diagram shown.

The sliding contacted is slided along the
potentiometer wire until zero reading is attained on
the galvanometer.

The e.m.f. of the cell will be proportional to the
potentiometer wire and given by the equation

e.m.f. of the cell = e.m.f. of the accumulator ×
XB
XY




However, the setup and operation of a potentiometer is not very convenient. A voltmeter or multimeter may be
used instead.

b) High impedance voltmeter / Digital multimeter

High impedance voltmeter or digital multimeter is not as good as potentiometer because the current flowing
through the cell would not be zero.

Although voltmeter and multimeter are not the ideal instruments for e.m.f. measurement, the operations of
them are very simple. Moreover, both of them have very high resistance and the current flowing through them
will be very minimal. The error will be within an acceptable level.


2. Use of salt bridge

Salt bridge is made by a thread of cotton soaked in saturated KNO
3(aq)
or NH
4
Cl
(aq)
solution. It is used to
complete the circuit when the two half cells are connected together.

a) Requirement of a salt bridge

Not all kind of strong electrolytes can be used as a salt bridge.

Criteria of a salt bridge
1. The electrolyte must have no reaction with the chemicals in the cell.

For example, NH
4
Cl
(aq)
salt bridge should not be used with Ag
(s)
| Ag
+
(aq)
system, otherwise precipitation
will occur.
Ag
+
(aq)
+ Cl
-
(aq)
→ AgCl
(s)


2. The cation and anion in the salt bridge should have the same migration speeds. If they have different
speeds, e.m.f. of the cell will be affected by the choice of salt bridge. For this reason, KNO
3(aq)
and
NH
4
Cl
(aq)
are the only two commonly used salt bridges.


III. Redox Equilibria Part 2 Page 3


b) An electrochemical cell does not need salt bridge

Salt bridge can be replaced by a porous partition if accurate supply of
e.m.f. is not required. The tiny holes allows the ions to diffuse slowly
but prevent the solutions from mixing.

Although the setup is more convenient than the one with the salt bridge,
it is not as good as salt bridge for two reasons.

1. The difference in diffusion speed of the ions in the two partitions
affects the e.m.f. of the cell.
2. After a long period of time, the two electrolytes may mix together
and an undesirable reaction may take place.
Daniel cell invented in 1837



Moreover, some electrochemical cells even do not require the used of a
porous partition.

For the redox reaction 2AgCl
(s)
+ H
2(g)
d 2Ag
(s)
+ 2HCl
(aq)


Reduction AgCl
(s)
+ e
-
d Ag
(s)
+ Cl
-
(aq)

Oxidation H
2(g)
d 2H
+
(aq)
+ 2e
-


Overall reaction 2AgCl
(s)
+ H
2(g)
d 2Ag
(s)
+ 2Cl
-
(aq)
+ 2H
+
(aq)


In this example the two half cells share the same electrolyte, HCl
(aq)
,
therefore, neither salt bridge nor porous pot is required.

3. Cell diagrams (IUPAC conventions)

Instead of drawing the actual diagram of an electrochemical cell, IUPAC has an agreed convention for writing an
notation, called cell diagram, to represent a cell.

In the notation,

| phase boundary (boundary between solid, liquid or gaseous phase)
|| or
MM
salt bridge
M
porous partition
, used to separate different species in the same phase
[ ] used to enclose different species in the same chemical system
+ used between different species in the same chemical system

N.B. The rule of writing of cell diagram is not very strict, it may be possible to construct more than 1 diagram
for 1 electrochemical cell.


III. Redox Equilibria Part 2 Page 4


Example 1

Example 2

Example 3

Zn
(s)
| Zn
2+
(aq)

M Cu
2+
(aq)
| Cu
(s)
Zn
(s)
| Zn
2+
(aq)
||
Cu
2+
(aq)
| Cu
(s)
Pt
(s)
| H
2(g)
| HCl
(aq)
| AgCl
(s)
| Ag
(s)






Example 1

For the Daniel cell with the porous partition

Zn
(s)
| Zn
2+
(aq)

M Cu
2+
(aq)
| Cu
(s)
e.m.f. of the cell = + 1.10 V

By convention, the sign of e.m.f. of a cell is given by the polarity of the
electrode at the right in a cell diagram.

Therefore, if the cell diagram is written as Cu
(s)
| Cu
2+
(aq)

M Zn
2+
(aq)
|
Zn
(s)
,
the e.m.f of the cell will become - 1.10 V.







Example 2

For the Daniel cell with salt bridge

Zn
(s)
| Zn
2+
(aq)
||
Cu
2+
(aq)
| Cu
(s)
e.m.f. of the cell = + 1.10 V

III. Redox Equilibria Part 2 Page 5


Example 3

Pt
(s)
| H
2(g)
| HCl
(aq)
| AgCl
(s)
| Ag
(s)
e.m.f of the cell = + 0.22 V

Sometimes " | " and " , " can be used interchangeably depending on
how do you define a phase.

AgCl
(s)
and Ag
(s)
can be considered as two different phases because
they are different substances. Therefore it is written as above.





Example 4

Electrochemical cell is not limited to metal |
metal ion system. For those system doesn't
involve metal, an inert electrode is required.
Graphite and platinum are the two commonly
used inert electrodes.

For the system doesn't involve metal, the cell
diagram is written in this way

(Pt) | Red
L
, Ox
L
|| Red
R
, Ox
R
| (Pt)

Red : Reduced form
Ox : Oxidized form


The two half-ionic equations involved in the cell on the right are

Reduction half equation MnO
4
-
(aq)
+ 8H
+
(aq)
+ 5e
-
d Mn
2+
(aq)
+ 4H
2
O
(l)

Oxidation half equation Fe
2+
(aq)
d Fe
3+
(aq)
+ e
-


The cell diagram is written as

C
(graphite)
| Fe
2+
(aq)
, Fe
3+
(aq)
|| [Mn
2+
(aq)
+ 4H
2
O
(l)
] , [MnO
4
-
(aq)
+ 8H
+
(aq)
] | C
(graphite)


Red
L
Ox
L
Red
R
Ox
R

Fe(II) Fe(III) Mn(II) Mn(VII)

N.B. " , " is used to used to separate different species in the same phase
" [ ] " is used to enclose used to enclose different species in the same chemical system

Glossary
electrochemical cell e.m.f potential difference potentiometer potentiometer wire
accumulator galvanometer impedance multimeter salt bridge migration speed
porous partition (pot) Daniel cell IUPAC cell diagram convention phase boundary
inert electrode half-cell half-ionic equation

Past Paper
Question
90 2A 1 b i ii iv
95 2A 3 c i ii iii
96 2A 3 a ii
97 2A 4 a ii iii

III. Redox Equilibria Part 2 Page 6
90 2A 1 b i ii iv
1b A cell based on the reaction:
6Fe
2+
(aq)
+ Cr
2
O
7
2-
(aq)
+ 14H
+
(aq)
→ 6Fe
3+
(aq)
+ 2Cr
3+
(aq)
+ 7H
2
O
(l)

consists of one platinum electrode dipped into a beaker containing an acidified solution of K
2
Cr
2
O
7(aq)
, and
another platinum electrode dipped into a separate beaker containing FeSO
4(aq)
, with the two solutions being
connected by a salt bridge.
With reference to this cell:

i write balanced equations for the reactions occurring at the cathode and the anode; 2
Reduction occurs at the cathode
Cr
2
O
7
2-
(aq)
+ 14H
+
(aq)
+ 6e
-
→ 2Cr
3+
(aq)
+ 7H
2
O
(l)
1 mark
Oxidation occurs at the anode
Fe
2+
(aq)
→ Fe
3+
(aq)
+ e
-
1 mark

ii state the direction in which electrons move when the electrodes are connected externally; 1
From anode to cathode 1 mark
iv represent the cell using the I.U.P.A.C. convention 2
Pt|Fe
2+
(aq)
,Fe
3+
(aq)
||Cr
3+
(aq)
,[Cr
2
O
7
2-
(aq)
,H
+
(aq)
]|Pt 2 mark
C i Many candidates did not give state symbols in the half equation.

95 2A 3 c i ii iii
3c The electromotive force of a new zinc-carbon dry cell is 1.5 V. When it is producing an electric current, the
following changes occur at the two electrodes:
Anode : Zn
(s)
reacts to give Zn
2+
(aq)
.
Cathode: MnO
2(s)
and NH
4
Cl
(aq)
react to give Mn
2
O
3(s)
and NH
3(g)
.

i Write half equations for the reactions at the anode and at the cathode, and the equation for the overall reaction that
occurs in the dry cell.
3
At anode Zn
(s)
→ Zn
2+
(aq)
+ 2e
-
1 mark
At cathode 2MnO
2(s)
+ 2NH
4
+
(aq)
+ 2e
-
→ Mn
2
O
3(s)
+ 2NH
3(g)
+ H
2
O
(l)
1 mark
or 2MnO
2(s)
+ NH
4
+
(aq)
+ 2e
-
→ Mn
2
O
3(s)
+ OH
-
(aq)
+ NH
3(g)

Overall equation
Zn
(s)
+ 2MnO
2(s)
+ 2NH
4
+
(aq)
→ Zn
2+
(aq)
+ Mn
2
O
3(s)
+ 2NH
3(g)
+ H
2
O
(l)
1 mark
or Zn
(s)
+ 2MnO
2(s)
+ NH
4
+
(aq)
→ Zn
2+
(aq)
+ Mn
2
O
3(s)
+ NH
3(g)
+ OH
-
(aq)


ii Write the cell diagram for the dry cell, using the IUPAC convention. 2
Zn
(s)
| Zn
2+
(aq)
| MnO
2(s)
| Mn
2
O
3(s)
| C
(s)
2 marks
or Zn
(s)
| Zn
2+
(aq)

M
NH
4
+
(aq)
| MnO
2(s)
| Mn
2
O
3(s)
| C
(s)

or Zn
(s)
| Zn
2+
(aq)
| [MnO
2(s)
+ NH
4
+
(aq)
], [Mn
2
O
3(s)
+ OH
-
(aq)
] | C
(s)

or Zn
(s)
| Zn
2+
(aq)
| [MnO
2(s)
+ 2NH
4
+
(aq)
], [Mn
2
O
3(s)
+ 2NH
3(aq)
] | C
(s)

(1 mark for the correct species at cathode and anode
½ mark for using vertical solid lines to indicate phase difference,
½ mark for using vertical double line (dotted line) to represent salt bridge
or using vertical single line to represent porous partition)

iii Explain why the electromotive force of the dry cell drops,
(1) after it has been used for some time;
(2) after it has been stored for a long time without being used.
3
(1)
If a current is drawn for some time, NH
3(g)
will accumulate at the cathode, the equilibrium will shift to the left,
leading to a drop in electrode potential. 1½ mark
OR
If a current is drawn for some time, Zn
2+
(aq)
will accumulate at the anode, the equilibrium will shift to the left,
making the electrode potential of Zn | Zn
2+
less negative.
(2)
If the cell is allowed to stand for some time, NH
4
+
which is an acid will react with Zn ½ mark
Zn
(s)
+ 2NH
4
+
(aq)
→ Zn
2+
(aq)
+ 2NH
3(aq)
+ H
2(g)
½ mark
or Zn
(s)
+ 4NH
4
+
(aq)
→ Zn(NH
3
)
4
2+
(aq)
+ 4H
+
(aq)
+ 2e
-

will decrease in [NH
4
+
(aq)
], the electrode potential will also drop. ½ mark

C As in previous years, this type of question on electrochemistry was poorly answered. The basic concept of the half
cell was not clearly understood by most candidates, hence they were not able to write the correct half equations
and the equation for the overall reaction. Many candidates could not write the IUPAC cell diagram for the zinc-
carbon dry cell.


96 2A 3 a ii
3a ii Consider the following electrochemical cell : 6
III. Redox Equilibria Part 2 Page 7

(1) Identify, with explanation, the negative terminal of the electrochemical cell.
(2) Comment on the change in concentration of Cu
2+
(aq)
ions in beakers D and E as electrochemical reaction
occurs.
(3) Using the IUPAC convention, write the cell diagram for the electrochemical cell.
(1) The left hand electrode / Cu electrode in beaker D is the negative terminal ½ mark

[Cu
2+
(aq)
] on LHS is lower than that on RHS / 1.0 M 1 mark
Oxidation occurs at left hand electrode / electrons flow from left hand electrode to right hand electrode
½ mark
so that [Cu
2+
(aq)
] in the beaker E decreases / the difference in [Cu
2+
(aq)
] of the two beakers becomes smaller.

(2) In beaker E, [Cu
2+
(aq)
] decreases because Cu
2+
is reduced to Cu ½ + 1 mark
or Cu
2+
(aq)
+2e
-
→ Cu
(s)


In beaker D, [Cu
2+
(aq)
] remains almost constant ½ mark
because Cu
2+
(aq)
ions produced in the electrochemical reaction combine with OH
-
(aq)
ions in the buffer to form
Cu(OH)
2(s)
1 mark

(3) Cu
(s)
| Cu(OH)
2(s)
| OH
-
(aq)
|| Cu
2+
(aq)
| Cu
(s)
1 mark
or Cu
(s)
| Cu(OH)
2(s)
| OH
-
(10
-4
M) || Cu
2+
(aq)
| Cu
(s)
(1 mark)
or Cu
(s)
| Cu
2+
(aq)
(2.0 × 10
-11
M) || Cu
2+
(aq)
(1.0 M) | Cu
(s)
(1 mark)
(Deduct ½ marks for each minor mistake)


97 2A 4 a ii iii
4a The diagram below shows an electrochemical cell connected to a digital voltmeter. An electromotive force of 0.83
V was recorded at 298K.

6
ii Write the overall equation for the electrochemical reaction.
iii Write the cell diagram for the electrochemical cell, using the IUPAC convention.

III. Redox Equilibria Part 3 Page 1
Topic III. Redox Equilibria Part 3

Reference
Reading

6.3.3


Assignment
Reading

Advanced Practical Chemistry, John Murray (Publisher) Ltd., 110–112, 176–177
A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 281–285
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 209–217
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 189–195

Syllabus
Electrode potentials
Standard hydrogen electrode
Relative electrode potential (Standard reduction potential)
Electrochemical series
Use of electrode potential

Notes
C. Electrode potentials

1. Standard hydrogen electrode

Since the actual e.m.f. of a cell is depending on both electrodes, the concentrations of electrolytes and
temperature. It would be more convenient if a standard condition is agreed and a reference electrode is chosen
for comparison.

Standard condition is defined as 1 atm, 298 K with all solution having molar concentration.

Hydrogen electrode is chosen by the scientist as the standard of reference.


It consists of an inert platinum electrode coated
with platinum black (platinum powder) which
increases the area of contact. The electrode is
enclosed in a hydrogen jacket at 1 atm and
immersed in a 1M H
+
(aq)
solution. Eventually, a
redox equilibrium is set up and can be described by
a half ionic equation.

2H
+
(aq)
+ 2e
-
d H
2(g)


If electron is supplied to the electrode, H
+
(aq)
will be
converted to H
2(g)
. Or, if electron is taken from the
electrode, H
2(g)
will be converted back to H
+
(aq)
.

Cell diagram of hydrogen electrode :
Pt
(s)
H
2(g)
| H
+
(aq)




III. Redox Equilibria Part 3 Page 2


2. Relative electrode potential (Standard reduction potential)

In order to compare the ease of losing or gaining electron of different chemical systems (different half cells),
hydrogen electrode is chosen arbitrarily as the standard of comparison. Standard hydrogen electrode is
assigned an (relative) electrode potential of 0 V. The values are also called reduction potentials because the
half equations are always expressed in reduction form when listed in the electrochemical series.

Reduction half equation 2H
+
(aq)
+ 2e
-
d H
2(g)
Eo = 0 V
oxidizing reducing
agent agent

At standard condition, the electrode potential measured is also called standard reduction potential.

Determination of relative electrode potential (standard reduction potential)
In the determination of the standard reduction potential of an unknown half cell, a cell with the hydrogen
electrode as the left-hand electrode and the unknown electrode as the right-hand electrode is set up. The e.m.f.
of the cell is then determined.



For example when the half-cell Pt|Cl
2(g)
|Cl
-(aq)
, is used
as the right-hand cell and the hydrogen electrode is
used as the left-hand cell, the e.m.f. is determined to
be 1.36 V.
However, a sign should be assigned to the e.m.f.
value to denote the direction of flow of electrode (i.e.
the relative affinity to electron). By definition, the
polarity of the right-hand electrode is assigned to the
e.m.f. value to do the job. Therefore, in this example,
the e.m.f. of the cell is +1.36 V

Cell diagram

Pt | H
2(g)
| H
+
(aq)
|| Cl
-
(aq)
| Cl
2(g)
| Pt
Eo = + 1.36 V



Furthermore, the relationship between the overall e.m.f. of a cell and the reduction potential of the 2 half cells
is given by

Eo
cell
= Eo
right
- Eo
left


When hydrogen electrode is chosen as the left-hand electrode, the value of Eo
left
will be zero.

Eo
cell
= Eo
right
- Eo
left
= Eo
right


Therefore, by definition, electrode potential of an electrode is given by the e.m.f. of the cell if the LEFT
electrode in the cell diagram is a hydrogen electrode.

Cl
2(aq)
+ 2e
-
d 2Cl
-
(aq)
Eo = + 1.36V


III. Redox Equilibria Part 3 Page 3


Consider another example where the positions of the
cell diagram and the physical setup are different.

Cell diagram

Pt | H
2(g)
| H
+
(aq)
|| Sn
2+
(aq)
| Sn
(s)
Eo = - 0.14 V

Sn
2+
(aq)
+ 2e
-
d Sn
(s)
Eo = - 0.14 V

N.B. When we are discussing the position of the
electrode, we are referring to the cell
diagram instead of the position of the actual
set up.



a) Meaning of sign and value

A positive electrode potential means that the electrode accepts electrons more readily than a hydrogen
electrode. As the sign and value of the electrode potential are depending on the readiness of a system to accept
/ donate electrons, electrode potential serves as a very good indicator of the oxidizing and reducing power of
different species.

When the reduction equations are listed according to the electrode potential, the list is called electrochemical
series.


III. Redox Equilibria Part 3 Page 4


3. Electrochemical series


Reduction equation Eo / V


Weak oxidizing agent Strong reducing agent

K
+
(aq)
+ e
-
d K
(s)
- 2.92

PbSO
4(s)
+ 2e
-
d Pb
(s)
+ SO
4
2-
(aq)
- 0.36

Sn
2+
(aq)
+ 2e
-
d Sn
(s)
- 0.14

2H
+
(aq)
+ 2e
-
d H
2(g)
0

4H
+
(aq)
+ SO
4
2-
(aq)
+ 2e
-
d H
2
SO
3(aq)
+ H
2
O
(l)
+ 0.17

AgCl
(s)
+ e
-
d Ag
(s)
+ Cl
-
(aq)
+ 0.17

PbO
2(s)
+ H
2
O
(l)
+ 2e
-
d PbO
(s)
+ 2OH
-
(aq)
+ 0.28

O
2(g)
+ 2H
2
O
(l)
+ 2e
-
d 4OH
-
(aq)
+ 0.40

2H
+
(aq)
+ O
2(g)
+ 2e
-
d H
2
O
2(aq)
+ 0.68

Ag
+
(aq)
+ e
-
d Ag
(s)
+ 0.80

2NO
3
-
(aq)
+ 4H
+
(aq)
+ 2e
-
d N
2
O
4(g)
+ 2H
2
O
(l)
+ 0.80

MnO
2(s)
+ 4H
+
(aq)
+ 2e
-
d Mn
2+
(aq)
+ 2H
2
O
(l)
+ 1.23

Cr
2
O
7
2-
(aq)
+ 14H
+
(aq)
+ 6e
-
d 2Cr
3+
(aq)
+ 7H
2
O
(l)
+ 1.33

Cl
2(aq)
+ 2e
-
d 2Cl
-
(aq)
+ 1.36

PbO
2(s)
+ 4H
+
(aq)
+ 2e
-
d Pb
2+
(aq)
+ 4H
2
O
(l)
+ 1.46

MnO
4
-
(aq)
+ 8H
+
(aq)
+ 5e
-
d Mn
2+
(aq)
+ 4H
2
O
(l)
+ 1.51

PbO
2(s)
+ SO
4
2-
(aq)
+ 4H
+
(aq)
+ 2e
-
d PbSO
4(s)
+ 2H
2
O
(l)
+ 1.69

MnO
4
-
(aq)
+ 4H
+
(aq)
+ 3e
-
d MnO
2(s)
+ 2H
2
O
(l)
+ 1.70

Strong oxidizing agent Weak reducing agent


N.B. The values are only correct at standard conditions.


The electrode potentials are measured at standard condition. If the condition is not standard, another value
would be expected.

For example, concentrated sulphuric acid has a concentration of about 18 M instead of 1 M.

Reduction potential of 1M H
2
SO
4(aq)
4H
+
(aq)
+ SO
4
2-
(aq)
+ 2e
-
d H
2
SO
3(aq)
+ H
2
O
(l)
Eo = +0.17 V

Concentrated sulphuric acid has a much more positive electrode potential and can be considered as a strong
oxidizing agent, while dilute sulphuric acid is not.




4. Use of electrode potential

a) Comparing the oxidizing and reducing power

On the electrochemical series, the chemical species are arranged according to their electrode potentials.

Those oxidizing agents low on the list accept electron readily and are strong oxidizing agents. e.g. MnO
4
-
/H
+
(aq)
.

And those reducing agents high on the list donate electron readily and are strong reducing agents. e.g. K
(s)
.



III. Redox Equilibria Part 3 Page 5


b) Calculation of e.m.f. of a cell

The e.m.f of a cell can be calculated from the values of the electrode potentials.

Consider an overall cell reaction,

Sn
(s)
+ 2Ag
+
(aq)
→ Sn
2+
(aq)
+ 2Ag
(s)


It is comprised two half cells presented by 2 half equations

Sn
2+
(aq)
+ 2e
-
d Sn
(s)
Eo = - 0.14 V
Ag
+
(aq)
+ e
-
d Ag
(s)
Eo = + 0.80 V

The electrode potential is reversed when the direction of reaction is reversed.

Sn
(s)
d Sn
2+
(aq)
+ 2e
-
Eo = + 0.14 V
Ag
+
(aq)
+ e
-
d Ag
(s)
Eo = + 0.80 V

The overall electrode potential can then calculated by adding the 2 values together.

Sn
(s)
+ 2Ag
+
(aq)
→ Sn
2+
(aq)
+ 2Ag
(s)
Eo = (+ 0.14 V) + (+ 0.80 V) = + 0.94 V


Or consider a cell diagram,

Sn
(s)
| Sn
2+
(aq)
|| Ag
+
(aq)
| Ag
(s)


The e.m.f. of the cell can be calculated by using the equation, Eo
cell
= Eo
right
- Eo
left


Sn
2+
(aq)
+ 2e
-
d Sn
(s)
Eo = - 0.14 V
Ag
+
(aq)
+ e
-
d Ag
(s)
Eo = + 0.80 V

Eo
cell
= Eo
right
- Eo
left
= (+ 0.80 V) - (- 0.14 V) = + 0.94 V

Since the sign of the e.m.f is depending on the direction of reaction of a cell, when a cell diagram is converted
to an equation or vice versa, the following convention should be observed.

Red
L
+ Ox
R
→ Red
R
+ Ox
L

Sn
(s)
+ Ag
+
(aq)
→ 2Ag
(s)
+ Sn
2+
(aq)
Eo = + 0.94 V


Furthermore, e.m.f. of a cell is depending on the nature of the two electrodes only. It is not depending on the
current (or no. of electrons) flowing through the circuit. In the calculation of e.m.f. of cell, the electrode
potentials are only simply added together and are not multiplied by the no. of electrons involved.

In contrast, in the balancing of a redox reaction, the half equations are multiplied whenever necessary to make
the no. of electrons conserve.

In the above example

Oxidation half ionic equation Sn
(s)
d Sn
2+
(aq)
+ 2e
-

Reduction half ionic equation Ag
+
(aq)
+ e
-
d Ag
(s)
× 2
-------------------------------------------
Overall ionic equation Sn
(s)
+ 2Ag
+
(aq)
→ Sn
2+
(aq)
+ 2Ag
(s)




III. Redox Equilibria Part 3 Page 6


c) Prediction of the feasibility of redox reaction


In general, oxidizing agent reacts with reducing
agent. Indeed, only strong oxidizing agent reacts
with strong reducing agent.

For example, both Cu
(s)
and Ag
(s)
are reducing
agents while Cu
2+
(aq)
and Ag
+
(aq)
are oxidizing
agents. But only Cu
(s)
reacts with Ag
+
(aq)
but Ag
(s)

doesn't reacts with Cu
2+
(aq)
.

Cu
2+
(aq)
+ 2e
-
d Cu
(aq)
Eo = + 0.34 V
Ag
+
(aq)
+ e
-
d Ag
(s)
Eo = + 0.80 V



Cu
(s)
+ 2Ag
+
(s)
→ Cu
2+
(aq)
+ 2Ag
(s)
Eo
cell
= (- 0.34 V) + (+ 0.80 V) = + 0.46 V (energetically feasible)
Cu
2+
(aq)
+ 2Ag
(s)
→ Cu
(s)
+ 2Ag
+
(s)
Eo
cell
= (+ 0.34 V) + (- 0.80 V) = - 0.46 V (energetically infeasible)

The reaction will only be energetically feasible if the sum of electron potentials is positive.

N.B. Relationship between ∆G and Eo is not required in A-Level)

When 1 e
-
jumps across a potential difference of 1V, the energy acquired by the electron is called 1 eV
(electron volt).

1 eV = 1.60 × 10
-19
C × 1 V = 1.60 × 10
-19
J

The e.m.f. of a cell is related to the ∆G by the expression,
∆Go = -nFEo
cell
where n is the no. of mole of e
-
involved,
F is the Faraday constant
Eo
cell
is the e.m.f. of the cell

∆Go is the total free energy change of the reaction. Its value is depending on the total no. of mole of
electron passing through the cell.

In contrast, Eo
cell
is a reflection of the electron pressure whose value is only depending on the nature of the
two electrode.

According to the expression ∆Go = -nFEo
cell
, a positive Eo
cell
means a negative ∆Go. This means an
energetically feasible reaction.

Note : ∆G = ∆H - T∆S = - RT ln K = - nFE

III. Redox Equilibria Part 3 Page 7


(1) Disproportionation reaction

Disproportionation – A process in which the same element undergoes oxidation and reduction
simultaneously.

e.g. 2Cu
+
(aq)
→ Cu
2+
(aq)
+ Cu
(s)




A chemical species will disproportionate if the reduction potential to the next lower oxidation state is more
positive than that from the next higher state. i.e. E
2
> E
1
.

Cu
+
(aq)
+ e
-
→ Cu
(s)
Eo = + 0.52 V
Cu
+
(aq)
→ Cu
2+
(aq)
+ e
-
Eo = - 0.15 V
----------------------------------------------------------------------------------------
2Cu
+
(aq)
→ Cu
(s)
+ Cu
2+
(aq)
Eo = + 0.37 V (energetically feasible)

Furthermore, it must be noticed that the overall reduction potential of Cu
2+
(aq)
to Cu
(s)
is not the sum of the
reduction potentials of the two steps. i.e. E
3
≠ E
1
+ E
2
. Two half-cell potentials cannot be added to give a
reduction potential for a different half-cell.

Glossary

standard hydrogen electrode e.m.f. reference electrode standard condition
platinum electrode relative electrode potential (standard reduction potential) electrochemical series
feasibility disproportionation

Past Paper
Question
90 1A 2 a 90 2A 1 b iii 90 2B 6 a ii
92 2A 1 c i
95 2B 6 c iii
96 2B 6 d i ii e
97 1A 2 c i ii 97 2A 4 a i
99 2A 1 b i ii

90 1A 2 a
2a A convenient laboratory method for determining electrode potentials makes use of a standard hydrogen electrode.
Draw a labelled diagram of a hydrogen electrode.
What conditions should be maintained when a hydrogen electrode is used as a standard hydrogen electrode? State
how the conditions can be met in the laboratory.
6

3 marks for correctly labelled diagram.
Deduct 1 mark for each wrong/missing label
Deduct ½ mark if ‘Platinized’ omitted
Conditions: Maintaining the stated conditions:
298K/25ºC thermostat/water-bath 1 mark
H
2
gas at 1 atm pressure pressure gauge 1 mark
[H
+
] = 1 M the use of standard acid solution 1 mark

C Diagrams of a hydrogen electrode were generally not well drawn. Only about a third of the candidates mentioned
the use of platinized platinum or platinum black, and even fewer considered the depth of its immersion in the
solution containing hydrogen ions.


III. Redox Equilibria Part 3 Page 8
90 2A 1 b iii
1b A cell based on the reaction:
6Fe
2+
(aq)
+ Cr
2
O
7
2-
(aq)
+ 14H
+
(aq)
→ 6Fe
3+
(aq)
+ 2Cr
3+
(aq)
+ 7H
2
O
(l)
consists of one platinum electrode dipped into a beaker containing an acidified solution of K
2
Cr
2
O
7(aq)
, and
another platinum electrode dipped into a separate beaker containing FeSO
4(aq)
, with the two solutions being
connected by a salt bridge. With reference to this cell:

iii calculate the e.m.f. of the cell, given that the standard reduction potentials of Fe
3+
/Fe
2+
and acidified Cr
2
O
7
2-
/Cr
3+

are respectively +0.77V and +1.33V; and
1
e.m.f. = +1.33 - (+0.77) = 0.56V 1 mark

90 2B 6 a ii
6a The following species are either impossible to prepare or very unstable. Explain, in each case, why this is so.
ii SI
6

S(VI) has a high redox potential and would oxidize I
-
to I
2
. SI
6
is therefore very unstable with respect to
disproportionation. 1½ mark


92 2A 1 c i
1c Given the following standard reduction potentials, Eo :
(Cr
2
O
7
2-
(aq)
+14H
+
(aq)
),(2Cr
3+
(aq)
+7H
2
O
(l)
)|Pt
(s)
1.33V
Cr
3+
(aq)
,Cr
2+
(aq)
|Pt
(s)
-0.41V
Zn
2+
(aq)
|Zn
(s)
-0.76V

i Predict the products of the reaction of zinc with dichromate(VI) solution. Explain your prediction. 3
In aqueous acid solution the overall reaction:
Zn
(s)
→ Zn
2+
(aq)
+ 2e
-

Cr
2
O
7
2-
(aq)
+ 14H+
(aq)
+ 6e
-
→ 2Cr
3+
(aq)
+ 7H
2
O
(l)

-------------------------------------------------------------------------------
Cr
2
O
7
2-
(aq)
+ 14H+
(aq)
+ 3Zn
(s)
→ 3Zn
2+
(aq)
+ 2Cr
3+
(aq)
+ 7H
2
O
(l)
Eo = -(-0.76) + 1.33 = 2.09 V
is favourable because of the large positive Eo value.
The overall reaction:
Zn
(s)
→ Zn
2+
(aq)
+ 2e
-

2e
-
+ 2Cr
3+
(aq)
→ 2Cr
2+
(aq)

-------------------------------------------------
2Cr
3+
(aq)
+ Zn(s) → Zn
2+
(aq)
+ 2Cr
2+
(aq)
Eo = - (-0.76) + (-0.41) = 0.35 V
is also favourable because of the positive Eo value. 2 marks
Therefore, the products are Zn
2+
(aq)
and Cr
2+
(aq)
. 1 mark

C i Candidates were not able to use all the given electrode potential data to predict the products : Zn
2+
and Cr
2+
.

95 2B 6 c iii
6c In aqueous solutions, TiO
2+
is colourless. It can be reduced to give a violet solution containing [Ti(H
2
O)
6
]
3+
.
iii The violet solution formed should be kept in a sealed vessel or handled in an inert atmosphere. Using the
following data, predict, giving a balanced equation, what will happen to the violet solution if it is not kept in a
sealed vessel or not handled in an inert atmosphere.
Eo / V
[Ti(H
2
O)
6
]
3+
(aq)
+ e
-
→ [Ti(H
2
O)
6
]
2+
-0.37
TiO
2+
(aq)
+ 5H
2
O
(l)
+ 2H
+
(aq)
+ e
-
→ [Ti(H
2
O)
6
]
3+
(aq)
+0.11
O
2(g)
+ 2H
2
O
(l)
+ 4e
-
→ 4OH
-
(aq)
+0.40
O
2(g)
+ 4H
+
(aq)
+ 4e
-
→ 2H
2
O
(l)
+1.23
4
From the Eo values, O
2
is a stronger [O] agent than TiO
2+
. 1 mark
At standard conditions, the Eo of the following reaction is +1.23 - (+ 0.11) V = +1.12 V 1 mark
4Ti
3+
+ O
2
+ 2H
2
O → 4TiO
2+
+ 4H
+
1 mark
Therefore, in the presence of oxygen, [Ti(H
2
O)
6
]
3+
will be oxidized to TiO
2+
(aq)
/ the violet solution will turn
colourless. 1 mark

C iii Candidates were expected to predict that if [Ti(H
2
O)
6
]
3+
is not kept in a sealed container, the reaction
4[Ti(H
2
O)
6
]
3+
+ O
2
→ 4TiO
2+
+ 4H
3
O
+
+ 18H
2
O takes place because the overall Eo for the reaction is +1.12 V.
However, most of them failed to do so.


96 2B 6 d i ii e
6d You are provided with the following standard reduction potentials :
Eo/V
Cu
2+
(aq)
+ e
-
d Cu
+
(aq)
+ 0.15
Cu
2+
(aq)
+ 2e
-
d Cu
(s)
+ 0.34

III. Redox Equilibria Part 3 Page 9
Cu
+
(aq)
+ e
-
d Cu
(s)
+ 0.52
I
2(s)
+ 2e
-
d 2I
-
(aq)
+ 0.54
Cu
2+
(aq)
+ I
-
(aq)
+ e
-
d CuI
(s)
+ 0.92

Using the above information
i explain why copper(I) compounds are unstable in aqueous solutions; and 2
In aqueous solutions, Cu
+
disproportionates to give Cu
(s)
and Cu
2+
(aq)
½ + ½ mark
2Cu
+
(aq)
→ Cu
(s)
+ Cu
2+
(aq)
(1 mark)
because the above reaction has a +ve Eº of + 0.52 - (+0.15) = + 0.37 V 1 mark

ii predict what will be observed when a potassium iodide solution is added to a copper(II) sulphate(VI) solution.
Explain your prediction and write a balanced equation for the reaction involved.
3
A brown solution and a (white) precipitate are formed because the reaction ½ + ½ mark
2Cu
2+
+ 4I
-
→ 2CuI + I
2
1 mark
has a Eº value of (0.92 - 0.54) = + 0.38 V 1 mark

6e In acidic conditions, VO
2
+
(aq)
can be reduced by sulphur dioxide to give VO
2+
(aq)
. Write a balanced equation for the
reaction.
2
VO
2
+
(aq)
+ 2H
+
(aq)
+ e
-
→ VO
2+
(aq)
+ H
2
O
(l)
½ mark
+) SO
2(g)
+ 2H
2
O
(l)
→ SO
4
2-
(aq)
+ 4H
+
(aq)
+ 2e
-
½ mark

---------------------------------------------------------------------------------------------

2VO
2
+
(aq)
+SO
2(g)
→ 2VO
2+
(aq)
+ SO
4
2-
(aq)
1 mark
(Award FULL marks if only the overall equation is given.)


97 1A 2 c i ii
2c Consider the standard reduction potentials listed below:
[FeF
6
]
3-
(aq)
+ e
-
d [FeF
6
]
4-
(aq)
Eº = + 0.40 V
I
2(aq)
+ 2e
-
d 2I
-
(aq)
Eº = + 0.54 V
Fe
3+
(aq)
+ e
-
d Fe
2+
(aq)
Eº = + 0.76 V
Explain the following observations, giving a balanced equation in each case.
4
i When Fe(NO
3
)
3(aq)
is added to KI
(aq)
, a brown solution is formed.
ii When concentrated KF
(aq)
is added to the resulting solution in (i) above, the brown colour fades.

97 2A 4 a i
4a The diagram below shows an electrochemical cell connected to a digital voltmeter. An electromotive force of 0.83
V was recorded at 298K.

6
i Write half-equations for the reaction at the anode and at the cathode, and give their corresponding standard
electrode potentials.


99 2A 1 b i ii
1b i What is 'standard reduction potential' ?
ii With reference to the standard reduction potentials listed below, explain why hydrochloric acid can be used to
acidify potassium dichromate(VI) solution but cannot be used to acidify potassium manganate(VII) solution. Give
a balanced equation for any reaction that takes place.
Eo/ V
Cr
2
O
7
2-
(aq)
+ 14H
+
(aq)
+ 6e
-
d 2Cr
3+
(aq)
+ 7H
2
O
(l)
+1.33
Cl
2(g)
+ 2e
-
d 2Cl
-
(aq)
+1.36
MnO
4
-
(aq)
+ 8H
+
(aq)
+ 5e
-
d Mn
2+
(aq)
+ 4H
2
O
(l)
+1.51


III. Redox Equilibria Part 4 Page 1
Topic III. Redox Equilibria Part 4

Reference
Reading

6.3.4

Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 288–290
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 217–219
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 196–198

Syllabus
D. Secondary cell and fuel cell

1. Lead-acid accumulator

Lead-acid accumulator is commonly used in vehicle to start the engine. Comparing with the other secondary
cell, it produces a much larger current.
Notes

The two electrodes are lead alloy grids filled
with spongy PbO
2(s)
(cathode) and spongy
Pb
(s)
(anode) immersed in the electrolyte of
dilute H
2
SO
4(aq)
. Upon discharge, thin layers
of PbSO
4(s)
will be coated on both the
cathode and anode. However, the reaction is
reversible. When the battery is charged up,
PbSO
4(s)
will be converted back to PbO
2(s)

and Pb
(s)
.

Question :
What would happen if a Daniel cell is
recharged ?


PbO
2
cathode (Reduction)
PbO
2(s)
+ 4H
+
(aq)
+ SO
4
2-
(aq)
+ 2e
-
→ PbSO
4(s)
+ 2H
2
O
(l)
Eo = + 1.69

Pb anode (Oxidation)
Pb
(s)
+ SO
4
2-
(aq)
→ PbSO
4(s)
+ 2e
-
Eo = + 0.36

Overall reaction Pb
(s)
+ PbO
2(s)
+ 2H
2
SO
4(aq)
d 2PbSO
4(s)
+ 2H
2
O
(l)
Eo
cell
= + 2.05 V

In a fully charged lead-acid accumulator, the 36% H
2
SO
4(aq)
has the density 1.27 gcm
-3
. Upon discharging,
H
2
SO
4(aq)
is consumed and H
2
O
(l)
is produced, the density of the electrolyte will decrease. The condition of
charge in the cell can be determined by measuring the density of the acid with a hydrometer.

Cell diagram Pb
(s)
| PbSO
4(s)
| H
2
SO
4(aq)
| PbSO
4(s)
| PbO
2(s)
| Pb
(s)

Red
L
Ox
L
Red
R
Ox
R

Pb(0) Pb(II) Pb(II) Pb(IV)

No salt bridge or porous partition is required because the two electrodes share the same electrolyte, H
2
SO
4(aq)
.



III. Redox Equilibria Part 4 Page 2


2. Hydrogen-oxygen fuel cell

Fuel cell is the battery used in spaceship to produce electricity.



H
2
Anode (Oxidation) H
2(g)
→ 2H
+
(aq)
+ 2e
-
Eo = 0 V

O
2
Cathode (Reduction) O
2(g)
+ 2H
2
O
(l)
+ 4e
-
→ 4OH
-
(aq)
Eo = + 0.40 V

Overall Reaction 2H
2(g)
+ O
2(g)
d 2H
2
O
(l)
Eo = + 0.40 V

On top of electrical energy, the fuel cell also provide the warmth and water for the astronaut in the spaceship.

Glossary
Secondary cell lead-acid accumulator alloy grid spongy hydrometer
hydrogen-oxygen fuel cell

Past Paper
Question
91 1A 2 a i ii iii
93 2A 1 c i ii iii
98 2A 4 a i ii iii

91 1A 2 a i ii iii
2a An electrochemical cell containing an oxygen cathode and a hydrogen anode is shown below :
The pistons above the gas chambers are frictionless.


i Write balanced equations for the half reactions and for the overall reaction in the cell. 2
cathode: 2H
+
+ ½O
2
+ 2e
-
d H
2
O
anode: H
2
d 2H
+
+ 2e
-

overall: H
2
+ ½O
2
→ H
2
O 2 marks
wrong coefficient -½
reverse labelling of cathode and anode reaction -½
wrong species in each reaction -½
wrong direction of reaction (e.g. if a single arrow) -½

III. Redox Equilibria Part 4 Page 3

ii How does the concentration of H
2
SO
4
affect the equilibria of the half reactions ? 1
↑[H
+
] will shift equilibrium of 2H
+
+ ½O
2
+ 2e
-
d H
2
O to right, and
shift equilibrium of H
2
d 2H
+
+ 2e
-
to left. ½ mark each

iii If weights are added to the pistons of both chambers, how would the reading of the voltmeter change ? Explain
your answer.
2
voltage reading increase 1 mark
pressure in O
2
and H
2
chamber increase or [O
2
] and [H
2
] increase ½ mark
equilibrium of H
2
+ ½O
2
→ H
2
O is shifted to right and favours the discharge of battery ½ mark

C Surprisingly, many candidates could not apply knowledge of chemical equilibria to an electrochemical reaction. A
fuel cell and an electrolytic cell could be the same problem if viewed from the equilibrium principles. Over half of
the candidates gave OH
-
as the product in one or both of the half reactions. They also confused the anode and the
cathode and the direction of overall reaction.


93 2A 1 c i ii iii
1c i Draw a labelled diagram of a cell that makes use of the reaction:
2H
2
SO
4(aq)
+ PbO
2(s)
+ Pb
(s)
→ 2PbSO
4(s)
+ 2H
2
O
(l)

Indicate the direction of electron flow on your diagram.
2


Labelled diagram 1 mark
Direction of electron flow 1 mark

ii Write a balanced equation for the reaction at each electrode. 2
At PbO
2
(cathode)
PbO
2(s)
+ HSO
4
-
(aq)
+ 3H
+
(aq)
+ 2e
-
→ PbSO
4(s)
+ 2H
2
O
(l)

or PbO
2(s)
+ 4H
+
(aq)
+ SO
4
2-
(aq)
+ 2e
-
→ PbSO
4(s)
+ 2H
2
O
(l)
1 mark
At Pb (anode)
Pb
(s)
+ HSO
4
-
(aq)
→ PbSO
4(s)
+ 2e
-
+ H
+

or Pb
(s)
+ SO
4
2-
(aq)
→ PbSO
4(s)
+ 2e
-
1 mark

iii Using the IUPAC convention, write the cell diagram for the above cell. 2
General format: (Pt)|Red
L
,Ox
L
||Red
R
,Ox
R
|(Pt)
Pb
(s)
|PbSO
4(s)
|H
2
SO
4(aq)
|PbSO
4(s)
|PbO
2(s)
|Pt
(s)

or Pb
(s)
|PbSO
4(s)
|H
2
SO
4(aq)
|PbO
2(s)
|PbSO
4(s)
|Pt
or PbSO
4(s)
|PbO
2(s)
|H
2
SO
4(aq)
|PbSO
4(s)
|Pb
(s)
(without physical state -1) 2 marks

C ii Many candidates had difficulties in writing balanced equations.
iii Few candidates gave the right cell diagram. Many candidates were not aware that in writing cell diagrams, a
vertical line " | ", instead of a comma ",", should be used to denote a phase boundary.


98 2A 4 a i ii iii
4a A lead-acid rechargeable cell is formed by dipping a lead plate coated with PbO
2(s)
and another lead plate coated
with PbSO
4(s)
in H
2
SO
4(aq)
.
8
i You are provided with the following standard reduction potentials at 298 K.

Eo/V
2H
2
O
(l)
+ 2e
-
d H
2(g)
+ 2OH
-
(aq)
- 0.83
PbSO
4(s)
+ 2e
-
d Pb
(s)
+ SO
4
2-
(aq)
- 0.36
Pb
2+
(aq)
+ 2e
-
d Pb
(s)
- 0.13
O
2(g)
+ 4H
+
(aq)
+ 4e
-
d 2H
2
O
(l)
+ 1.23
PbO
2(s)
+ SO
4
2-
(aq)
+ 4H
+
(aq)
+ 2e
-
d PbSO
4(s)
+ 2H
2
O
(l)
+ 1.69

(I) Write half-equations for the reaction at the anode and at the cathode of the cell.
(II) Write the overall equation for the electrochemical reaction and hence determine the standard electromotive
force (e.m.f.) of the cell.

III. Redox Equilibria Part 4 Page 4
ii Write the cell diagram in accordance with the IUPAC convention.
iii Explain why
(I) the voltage of the cell drops upon discharge:
(II) the cell is rechargeable.


III. Redox Equilibria Part 5 Page 1
Topic III. Redox Equilibria Part 5

Reference
Reading
6.3.5


Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 516–518
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 309–310
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 271–272

Syllabus

Corrosion of iron and its prevention
Notes
E. Corrosion of iron and its prevention

1. Electrochemical process of rusting

Formation of rust is a complicate process. Rusting only occurs when iron gets in contact with dissolved
oxygen in water.

Rusting can be considered as an electrochemical process. Initially, Fe
(s)
atom loses 2 electrons and becomes
Fe
2+
(aq)
ion.

Anode (oxidation) Fe
(s)
→ Fe
2+
(aq)
+ 2e
-
Eo = + 0.44 V

The dissolved oxygen in water accepts the electrons and becomes hydroxide ion.

Cathode (reduction) O
2(aq)
+ 2H
2
O
(l)
+ 4e
-
→ 4OH
-
(aq)
Eo = + 0.40 V

The overall e.m.f. of the cell = (+ 0.44 V) + (+ 0.40 V) = + 0.84 V (energetically feasible)


Fe
2+
(aq)
precipitates with OH
-
(aq)
ion in water to form solid iron(II) hydroxide..

Fe
2+
(aq)
+ 2OH
-
(aq)
→ Fe(OH)
2(s)



Iron(II) hydroxide is then further oxidized by the dissolved oxygen to iron(III) hydroxide.

4Fe(OH)
2(s)
+ O
2(aq)
+ 2H
2
O
(l)
→ 4Fe(OH)
3(s)


Upon standing, the iron(III) hydroxide changes to a reddish brown solid – rust, Fe
2
O
3
·nH
2
O
(s)
.

Since Fe
2
O
3
·nH
2
O
(s)
has a very loose structure, it flakes off from the iron surface and exposes the inside of the
iron block to further corrosion.

Because rusting involves flowing of charges, rusting would be faster in the presence of an electrolyte. i.e. iron
rusts much faster in sea water (sodium chloride solution) than in distilled water. Acidic condition also
accelerates rusting by reacting with iron metal.
III. Redox Equilibria Part 5 Page 2


Rust indicator - Potassium hexacyanoferrate(III)


Since Fe
2+
(aq)
ion is the one of the initial product in rusting,
formation of rust can be monitored by detecting the presence of
Fe
2+
(aq)
ion. Potassium hexacyanoferrate(III), K
3
Fe(CN)
6(aq)
, is
a yellow chemical which turns deep blue in the presence of
Fe
2+
(aq)
ion. It serves as a very good indicator of rust.

[Fe(CN)
6
]
3-
(aq)
+ Fe
2+
(aq)
→ [FeFe(CN)
6
]
-
(aq)

yellow deep blue



When a drop of solution containing phenolphthalein and potassium
hexacyanoferrate(III) is dropped onto an iron surface, the rim of the
drop will turn pink and the center of the drop will turn blue gradually.

This shows that the rim is the cathodic area where the concentration of
dissolved oxygen is higher. And, the center is the anodic area.

After a long time, most rust will form somewhere between the cathodic
area and anodic area, where Fe
2+
and OH
-
ion meet..


2. Prevention of rusting

a) Coating

Since rust is only formed in the presence of oxygen and water, iron can be protected from rusting by putting a
coating on the surface.

A. Paint or grease
Painting is the most cost effective method for large iron object but if the painted surface is scratched, iron will
be vulnerable.
Grease or oil is used in the moving part of machinery where the paint will be scratched.

B. Galvanising (zinc dipping)
Iron is dipped into a tank of molten zinc or molten zinc is spray onto iron so that the surface of the iron is
coated with a layer of zinc. The process is called galvanising or galvanization. The iron is called galvanised
iron. Although zinc also reacted with oxygen in the air to form zinc oxide, zinc oxide has a very tight structure
and protects the zinc underneath from further corrosion.

The body of most automobiles are galvanized before the paint is applied. This make it more resistant to
rusting.


C. Tin-plating
Since zinc is toxic, it is not used in protecting the food can from rusting. Instead, a layer of tin is coated on the
surface of iron can to exclude the air and water. However, if the tin-plating is scratched and the iron
underneath is exposed, the tin-plated can will rust even faster than an ordinary iron can. This is because iron is
more reactive than tin and iron will lose electrons through tin quickly.



III. Redox Equilibria Part 5 Page 3


D. Electroplating of other metal
Chromium is another metal which is coated on iron to prevent rusting. Chromium is frequently used because
of its silvery appearance. e.g. Most water taps are electroplated with chromium.


b) Sacrificial Protection

Iron is first changed to iron(II) ion in the rusting process. If the formation of iron(II) ion can be suppressed,
iron can be protected from rusting.

Fe
(s)
d Fe
2+
(aq)
+ 2e
-


A reactive metal loses electron more readily than a less reactive metal. By connecting iron to a more reactive
metal, formation of Fe
2+
(aq)
can be retarded. Once a Fe
2+
(aq)
ion is formed, it will acquire the electrons from the
more reactive metal and changes back to Fe. Consequently, iron is protected from corrosion but the more
reactive metal is sacrificed instead.

This method is preferable for the iron object which is hard to be repainted e.g. iron pipe under the ground, hull
of ship.





Sacrificial protection by galvanization

Besides isolating iron from air and water, Zn
(s)
also protects iron by sacrificial protection because Zn
(s)
is more
reactive than Fe
(s)
.

For the same reason, the body of a car is always connected to the negative terminal of the car battery. This
make the car body negatively charged and less vulnerable to rusting.

c) Alloying

Pure iron rust easily in moist air. But if appropriate amounts of carbon, chromium and nickel are added, iron
will become stainless steel which is more resistant to rusting.

Glossary
rusting (corrosion of iron) rust (hydrated iron(III) oxide) anodic area cathodic area
rust indicator (potassium hexacyanoferrate(III)) coating galvanising zinc dipping
sacrificial protection tin-plating electroplating alloying

Past Paper
Question
97 2A 4 b i ii
99 2A 1 b iii


97 2A 4 b i ii
4b Discuss and write relevant equations for the electrochemical processes involved when broken surfaces of the
following are exposed to moist air.

i galvanized iron
ii tin-plated iron

99 2A 1 b iii
1b iii Explain why cathodic protection can be used to prevent the corrosion of iron. (7 marks)


Phase Equilibria


I. One component system
A. Water
1. Phase diagram of water
2. Isotherm of water
3. PVT surface of water
B. Carbon dioxide
1. Phase diagram of carbon dioxide
2. Isotherm of carbon dioxide
II. Two components system
A. Ideal system
1. Raoult's law
2. Composition of the liquid mixture comparing with composition of the vapour
3. Boiling point-composition diagram
a) Definition of boiling point
b) Boiling point-composition diagram
c) Fractional distillation
B. Non-ideal solution
1. Deviation from Raoult's law
a) Positive deviation
b) Negative deviation
c) Enthalpy change of mixing
2. Elevation of boiling point and depression of freezing point by an involatile solute
3. Boiling point of two immiscible liquid
a) Steam distillation

III. Three components system
A. Partition of a solute between two phases
1. Solvent extraction
a) Calculation
2. Paper chromatography
a) R
f
value
b) Separation of amino acids
Phase Equilibria Unit 1 Page 1
Topic Phase Equilibria Unit 1

Reference
Reading

7.1


Assignment
Reading

A-Level Chemistry (3rd ed.). Stanley Thornes (Publisher) Ltd., 239–240

Syllabus
One component system
PVT surface
Phase diagram
Isotherm

Notes
I. One component system

One component system is a system consists of one substance.


At different condition, the same substance may have different
physical state or phase. There are 3 physical states : solid, liquid
and gas.

Moreover, the same substance with the same physical state may not
be exactly the same. e.g. graphite and diamond are two allotropes of
carbon, the two different phases of solid carbon. Diatomic oxygen
and ozone is another pair of example.


By measuring the physical properties of a substance at different pressure, volume and temperature, a PVT surface
can be constructed. Different regions of the surface represents different phases of a substance. PVT surface is
solely a summary of experimental findings and can only be obtained through experiment.



Phase Equilibria Unit 1 Page 2


Depending on the properties, gaseous phase can be further divided into vapour and gaseous phases.
Vapour is defined as a gas which can be liquefied by compression alone. Conversely, a gas cannot be compressed
into liquid without cooling.


However, it is rather difficult to study pressure, volume and temperature altogether. It would be easier to
investigate a 2-dimensional projection of the 3-dimensional PVT surface along the temperature or volume axes.

The projection along the volume axis is called phase diagram.
The projection along the temperature axis is called isotherm.


A. Water

1. Phase diagram of water

A solid line on the diagram represents the condition at
which two phases coexist.

The temperature at which solid and liquid coexist is called
melting point.
The temperature at which liquid and gas coexist is called
boiling point.
The temperature at which solid and gas coexist is called
sublimation point.

The point where the 3 solid lines joined together is called
triple point. It is the only condition at which solid, liquid
and gaseous phases can coexist in equilibrium. It is an
unique condition for a specific substance.

For example, 6.03 × 10
-3
atm and 273.16 K for water
5.11 atm and 216.6 K for carbon dioxide.
Phase diagram of water
BD – melting/freezing curve
AB – sublimation curve
BC – vaporization/condensation curve
EB – supercooling curve



Water is a very special substance which expands upon freezing. Its freezing curve (BD) has a negative slope.
Comparatively, carbon dioxide has a freezing curve with positive slope.

The freezing curve (BD) represents the conditions at which water and ice are at equilibrium. i.e. melting point of
ice at different pressure.

From the negative slope of the freezing curve, it can be seen that the melting point decreases with increasing
pressure. If pressure is exerted onto a cube of ice, it will melt because the freezing point of water is lowered.

But, how is this related to the volume of ice ? This can be explained by Le Chatelier's principle.

Water (liquid) d Ice (solid)
higher density lower density
(smaller volume) (larger volume)

When pressure is exerted onto ice, the system will response in a way so that the effect of increased pressure can be
reduced. This is done by converting ice to water which has lower volume. Once the pressure is removed, water will
freeze again. At molecular level, when a high pressure is exerted onto ice, the open structure will be broken and ice
will be converted to water.

Like all kind of change, freezing process also involves activation energy, though it is very small comparing with
other chemical process. If a beaker of water is cooled calmly, it may reach a temperature below 0ºC without
freezing. The liquid water which has a temperature lower than 0ºC is called supercooled liquid. If the supercooled
water is disturbed (i.e. activation energy is provided), the water will freeze immediately. The curve EB represents
the supercooling curve of water. The existence of water extends into the ice region..

Supercooled water is energetically less stable than ice. Supercooled water is a metastable state, which means highly
unstable.
Phase Equilibria Unit 1 Page 3


2. Isotherm of water


Isotherm is the curve representing the relationship between
the pressure and volume of a substance at the same
temperature.

The isotherm has the shape of a hyperbola only at high
temperature. This means that the pressure is inversely
proportional to volume (i.e. P α
1
V
which is stated by
Boyles' Law). At high temperature, the gaseous molecules
are moving at great speed. The intermolecular attractions
among particles become insignificant comparing with
thermal motions. This makes a gas behave as an ideal gas.

At a temperature higher than the critical temperature, a gas
cannot be liquefied by compression alone. This has
important implication in the manufacturing of liquid air. If
the temperature is too higher, the air can never be
compressed into liquid no matter how high the pressure is.


At a temperature lower than critical temperature, vapour can be compressed into liquid. The vapour pressure, at
which the vapour and liquid coexist, is called saturated vapour pressure.
Saturated vapour pressure is a quantity independent of volume. If the volume of the system is decreased, more
vapour will condense into liquid and the saturated vapour pressure will remain unchanged. It is only depending on
temperature.

Water vapour d Liquid water



3. PVT surface of water


The curve abcdef represents the change of water when it
is warmed at 1 atm pressure.
Along ab, ice expands a little bit.
Along bc, ice starts to melt and contract. Ice and water
coexist at melting point.
Along cd, water is heated up and expands.
Along de, water boils and turns to water vapour. Water
and water vapour coexist at boiling point.
Along ef, the temperature and volume of water vapour
increase. At a temperature beyond critical temperature,
it becomes a gas.

The curve ghjk represents the compression of water
vapour to liquid water at room temperature.

The curve nopqrs represents the compression of water
vapour at a temperature lower than triple point
temperature.
Along no, the vapour is compressed.
Along op, the vapour sublimes directly into ice.
Along pq, ice is compressed and the volume gets a little
bit small.
Along qr, ice melts because of the increasing pressure.
Along rs, liquid water is compressed and the volume
change is very minimal.

PVT surface of water
Phase Equilibria Unit 1 Page 4


B. Carbon dioxide


Liquid carbon dioxide doesn't exist at atmospheric pressure. From the phase diagram of carbon dioxide, the triple
point pressure (5.1 atm) is higher than atmospheric pressure. When dry ice is warmed, it sublimes directly to
carbon dioxide gas.

Carbon dioxide behaves like many other substances. It contracts upon freezing and has a freezing curve with a
positive slope.


1. Phase diagram of carbon dioxide



2. Isotherm of carbon dioxide



Glossary
one component system sublimation phase allotrope PVT surface vapour gas
projection phase diagram isotherm triple point freezing curve sublimation curve
vaporization curve supercooled liquid supercooling curve metastable state hyperbola
ideal gas critical point vapour pressure (saturated) vapour pressure

Past Paper
Question
90 1A 2 e i ii iii
92 1A 2 g i ii iii iv
98 1A 2 a i ii iii

90 1A 2 e i ii iii
2e

Each of the graphs A to D in the above diagram shows the variation of pressure with volume for a particular
substance at different temperatures T
1
, T
2
, T
3
and T
4
.

i Name the point P and comment on its significance. 1½
Critical point ½ mark
At points on isotherm above P, the gaseous state of the substance cannot be liquefied by the increased in pressure
alone. 1 mark

Phase Equilibria Unit 1 Page 5

ii What is the significance of the horizontal portion of graph D? 1
Along the horizontal portion, the gaseous and liquid states of the substance can co-exist. 1 mark
Or
The horizontal portion signifies the liquefaction (vaporization) of the gaseous (liquid) state of the substance.

iii Which graph provides experimental evidence that PV = nRT? Explain your answer. 1½
Graph A ½ mark
Q it has the shape of a hyperbola 1 mark
or
Q it represents the relationship that P is inversely proportional to 1/V.

C iii Candidates were expected to know that Graph A provides experimental evidence that PV = nRT because the graph
gives the relationship in the form of a hyperbola in which P is inversely proportional to V (at a given temperature).


92 1A 2 g i ii iii iv
2g For the phase diagram below:


i Identify the point X and Y. 1
Point X - critical temperature (substance can no longer exist in the liquid state beyond this temperature) ½ mark
Point Y - triple point (solid, liquid and vapour are all at equilibrium) ½ mark

ii Which two points in the diagram define the sublimation curve? 1
Y, Z
iii Mark on the diagram, using the symbol B, the normal boiling point. 1

Point B is the boiling point. 1 mark

iv Suggest the meaning of the curve YW. 1
Metastable state or Supercooling occurs. 1 mark

98 1A 2 a i ii iii
2a The phase diagram for carbon dioxide is shown below.
Phase Equilibria Unit 1 Page 6

i Identify points B and C. 1
ii What is the physical meaning of point C ? 1
iii Starting with a sample of CO
2(g)
at room temperature and atmospheric pressure, suggest how the following can be
obtained.
(I) solid CO
2
(dry ice)
(II) liquid CO
2

2

Phase Equilibria Unit 2 Page 1
Topic Phase Equilibria Unit 2

Reference
Reading
7.2.1
Modern Physical Chemistry ELBS pg. 372–377


Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 181–186

Syllabus

Two components system
Ideal system
Raoult's law

Notes
II. Two components system

Two components system is a system consists of 2 different substances.

If a system is comprised of one more substance, the physical behavior will be more complicate. On top of
pressure, volume and temperature, the physical properties of a mixture is also depending on the relative
abundance (mole fraction) of individual component. A 4-dimensional space will be required to represent the
experimental findings.

It would be easier if the investigation is limited to a given temperature. Therefore, the effect of
temperature can be excluded. The situation can further be simplified by considering the liquid and
vapour phases only.


The saturated vapour pressure of a liquid is also commonly known as the vapour pressure of the liquid. In the
presence of a liquid, the saturated nature of the vapour is understood.


At a given temperature in an one component
system, the (saturated) vapour pressure is a
constant independent of volume. If the volume of
the mixture is decreased, some vapour will be
compressed into liquid and the (saturated) vapour
pressure will remain a constant.

Liquid d Saturated vapour

In general, the more volatile a liquid, the higher
will be the (saturated) vapour pressure at a given
temperature.



However, if two volatile liquids are mixed, the
(saturated) vapour pressure will no longer depend
on temperature only. It will also be depending on
the abundance of individual component.

P
A
º = vapour pressure of pure A (more volatile)
P
B
º = vapour pressure of pure B (less volatile)

Phase Equilibria Unit 2 Page 2


By Dalton's law of partial pressure,

Total vapour pressure = partial pressure of vapour A + partial pressure of vapour B

P
T
= P
A
+ P
B



A. Ideal system

It is found that if the intermolecular forces among all molecules in a mixture have similar magnitude, i.e. the
intermolecular forces ALA, ALB and BLB are all similar, the (saturated) vapour pressure will be jointly
proportional to the mole fractions of the two components.

The ideal behavior of the solution is further confirmed by the nearly zero enthaply change of mixing of the two
components.




1. Rauolt's Law

The system in which the total (saturated) vapour
pressure is jointly proportional to the mole fractions
of the two components is called an ideal system.

The relationship P
A
= X
A
× P
A
º is called Raoult's
law.

Or in words, the partial vapour pressure of any
volatile component of an ideal solution is equal to
the vapour pressure of the pure component
multiplied by the mole fraction of that component
in the solution.

N.B. Meaning of superscript
º : pure substance
o : standard state

Vapour pressure-composition diagram


By Dalton's law of partial pressure,

Total vapour pressure = partial pressure of vapour A + partial pressure of vapour B

P
T
= P
A
+ P
B


mole vapour mole vapour
= fraction of × pressure of + fraction of × pressure of
component A pure A component B pure B

P
T
= X
A
× P
A
º + X
B
× P
B
º

A vapour pressure-composition curve can also be considered as a kind of phase diagram. At an external
pressure higher than the equilibrium vapour pressure, the vapour will tend to condense to form more liquid.
And if the external pressure is lower than the equilibrium vapour pressure, the liquid will tend to vaporize to
form more vapour.
Phase Equilibria Unit 2 Page 3


2. Composition of the liquid mixture comparing with composition of the vapour


Will the composition of the vapour be the same as
the composition of the liquid ?

Obviously, the more volatile component vaporizes
more easily and will have a greater contribution in
the total vapour pressure (which is related to
concentration) at a certain temperature. Therefore,
when an equal molar solution of 2 liquids
evaporates, the vapour will be enriched by the
vapour of the more volatile component.

Quantitatively, the composition of the vapour of an
ideal solution at a given temperature can be
calculated according to Rauolt's law.

This requires the liquid composition of the mixture
and the (saturated) vapour pressure of individual
component at the given temperature.

Mole fraction of A in the liquid = X
A
Mole fraction of B in the liquid = X
B
= (1- X
A
)
Partial vapour pressure of A = P
A
= X
A
P
A
º
Partial vapour pressure of B = P
B
= X
B
P
B
º
Vapour pressure-composition diagram



Vapour pressure of the liquid mixture (according to Rauolt's law)
= P
T
= X
A
P
A
º + X
B
P
B
º = X
A
P
A
º + (1- X
A
)

P
B
º

Mole fraction of A in the vapour (according to Dalton's law of vapour pressure)
= X
A
' =
P
A
P
A
+ P
B
=
X
A
P
A
º
X
A
P
A
º + X
B
P
B
º
=
X
A
P
A
º
X
A
P
A
º + (1 - X
A
)P
B
º


Data
(Saturated) vapour pressure of A at 300 K = 1.0 × 10
4
Pa
(Saturated) vapour pressure of B at 300 K = 3.0 × 10
3
Pa

Calculation

Determine the composition of the vapour of the equimolar mixture of A and B at 300 K.















By repeating the calculation for the mixtures with different compositions, a vapour composition curve can be
constructed on the same vapour pressure-composition diagram.

Phase Equilibria Unit 2 Page 4


3. Boiling point composition diagram

a) Definition of boiling point

A liquid is said to be boiling when the (saturated) vapour pressure reaches the atmospheric pressure. A more
volatile liquid has a higher (saturated) vapour pressure at a given temperature, thus it has a comparatively
lower boiling point.

b) Boiling point-composition diagram


By measuring the boiling pointsof mixtures with
different composition and the composition of the
vapour, a boiling composition diagram can be
constructed.

A boiling point composition diagram also consists
of 2 lines. The first one is the boiling point of the
mixture with different composition. The second one
is the composition of the vapour when the mixture
boils.

The diagram on the right is the boiling point-
composition diagram of an ideal system consisting
of propan-1-ol and 2-methylpropan-1-ol.


Mole fraction of propan-1-ol
in the liquid
(prepared experimentally)
Boiling point of the mixture
/ ºC
(measured)
Boiling point of the distillate
/ ºC
(measured)
Mole fraction of propan-1-ol
in the vapour
(read from the graph)
A 0 109.0 109.0 0
B 0.10 105.2 99.1 0.24
C 0.20 100.9 94.2 0.41
D 0.30 97.4 91.3 0.53
E 0.40 94.3 88.6 0.65
F 0.50 92.0 86.8 0.74
G 0.60 89.5 85.3 0.82
H 0.70 87.3 84.4 0.90
I 0.80 85.6 84.0 0.94
J 0.90 84.2 83.7 0.98
K 1 83.3 83.3 1


Actually, it is quite difficult to determine the composition of the vapour chemically. It would be more convenient
to determine the boiling point of the distillate (condensed from the vapour) and determine the composition of the
vapour using the liquid composition curve as the calibration curve.

(The boiling point composition curve cannot be constructed from the Rauolt's law, Rauolt's law does not provide
any relationship between the vapour pressure and the temperature. It only provides the relationship between
vapour pressure and mole fraction of the liquid.)


Phase Equilibria Unit 2 Page 5


c) Fractional distillation


The boiling point composition
curve can be used to predict the
purity of the distillate.

For example, when a mixture of
0.2 mole propan-1-ol and 0.8 mole
2-methylpropan-1-ol is boiled,
from the curve, the vapour will
have 0.37 mole of propan-1-ol and
0.63 mole of 2-methylpropan-1-ol.
The distillate will have the same
composition as the vapour.

It should be noted that boiling is a
constant temperature process, in
which the liquid mixture and the
vapour will have the same
temperature (Line CD). On the
other hand, condensation of the
vapour is accompanied with a
decrease in temperature. (Line DE)

If the 0.37 mole propan-1-ol and
0.63 mole 2-methylpropan-1-ol
mixture is distilled again, from the
curve, the distillate obtained will
have 0.58 mole propan-1-ol and
0.42 mole 2-methylpropan-1-ol.

If the distillation is continued, the
final distillate will be 100%
propan-1-ol.




While more propan-1-ol is removed, the percentage of the less volatile 2-methylpropan-1-ol remain in the
flask will increase. As a result, the boiling point of the liquid will increase gradually.

Instead of separate distillations, successive distillations can be accomplished by using a fractionating column,
thus fractional distillation.

Upon heating, the liquid mixture vaporizes and condenses on the glass beads when it moves further from the
heat source. The thin liquid film condensed on the glass bead will evaporate again while more hot vapour is
coming up and the distillation will continue.

In general, in the fractionating column, the composition will change when a liquid mixture is vaporized but the
composition will not change when a vapour mixture is condensed.

Glossary
two components system 4-dimensional space (saturated) vapour pressure jointly proportional
Rauolt's law ideal system/solution vapour pressure-composition diagram liquid composition curve
vapour composition curve boiling point composition diagram boiling point fractional distillation
fractionating column glass bead boiling process condensation process liquid film

Past Paper
Question
91 2A 3 b i ii
93 2A 1 a i ii
94 2A 2 c i
95 2A 1 c i
96 2A 2 c i
99 2A 2 a i ii

91 2A 3 b i ii
Phase Equilibria Unit 2 Page 6
3b i A liquid is added as a solute to a solvent forming an ideal solution. Comment on the vapour pressure of the
solution as compared with that of the pure solvent.
3
If a volatile solute is added to a solvent, the total vapour pressure will be the sum of the partial pressures of the
solute and solvent. If the vapour pressure of the solute is higher than the vapour pressure of the solvent then the
total vapour pressure is higher and vice versa. 3 marks

ii The vapour pressures of pure methanol and ethanol at 25ºC are 89.2 mm Hg and 44.6 mm Hg respectively., A
mixture containing 32.0 g of methanol and 184.0 g of ethanol behaves as an ideal solution. Calculate the partial
vapour pressure of each component, the total vapour pressure of the mixture and the composition of the vapour.
(Relative atomic masses : H, 1.0; C, 12.0; O, 16.0)
4
CH
3
OH mol. wt. = 32
C
2
H
5
OH mol. wt. = 46
No. of moles of CH
3
OH =
32
32
= 1
No. of moles of C
2
H
5
OH =
184
46
= 4
Mole fraction of CH
3
OH =
1
5
= 0.2
Mole fraction of C
2
H
5
OH =
4
5
= 0.8 1 mark
By Raoult’s Law P
A
= x P
A
º 1 mark
Partial pressure of CH
3
OH =
1
5
× 89.2 = 17.84 mmHg
Partial pressure of C
2
H
5
OH =
4
5
× 44.6 = 35.68 mmHg 1 mark
Total vapour pressure = 17.84 + 35.68 = 53.52 mmHg ½ mark
The composition of CH
3
OH in the vapour =
17.84
53.53
=
1
3

The composition of C
2
H
5
OH in the vapour = 1 -
1
3
=
2
3
½ mark
i.e. ratio of CH
3
OH : C
2
H
5
OH is 1 : 2

C i Most candidates were not able to point out that the vapour pressure of the solution could be higher or lower than
that of the pure solvent.

ii Careless mistakes in the calculation of mole fractions were common.

93 2A 1 a i ii
1a Liquid A is miscible with Liquid B over the whole composition range, forming ideal solutions. The vapour
pressures of pure A and pure B, measured at 350 K, are 24.0 kPa and 12.0 kPa respectively.

i Calculate the vapour pressure of a liquid mixture consisting of 60 mole % A and 40 mole % B at 350 K. 3
P
A
= P
A
ºX
A

P
B
= P
B
ºX
B
1 mark
Partial pressure of A = 24 × 0.6 = 14.4 kPa
Partial pressure of B = 12 × 0.4 = 4.8 kPa 1 mark
Total vapour pressure P
T
= 14.4 + 4.8 = 19.2 kPa (wrong unit -½) 1 mark

ii The mixture in (i) is distilled at 350 K and a small amount of the distillate is collected. If this distillate is distilled
for a second time at 350 K, calculate the composition of the first droplet of the second distillate.
4
Composition of distillate (1st time)
X
A
=
P
A
P
T
=
14.4
19.2
= 0.75
X
B
= 1 - 0.75 = 0.25 1 mark
Total vapour pressure of second distillation = 0.75 × 24 + 0.25 × 12 = 21 kPa 1 mark
Composition of second distillate
X
A
=
0.75 × 24
21
= 0.86 1 mark
X
B
= 1 - 0.86 = 0.14 1 mark

C ii Many candidates were not able to get the final answers correct because they did not realise that the ratio of partial
pressures of A to B in the first distillate was the same as the mole ratio of A to B in the condensed phase. This
indicated that the underlying principles of fractional distillation were not well understood by these candidates.


Phase Equilibria Unit 2 Page 7
94 2A 2 c i
2c Two miscible liquids E and F form ideal solutions on mixing. At 298 K, the vapour pressure E is p
0
while that of
pure F is 2p
0
.

i Sketch a graph of vapour pressure versus mole fraction for the above solutions at 298K. For a mixture of E and F
with mole ration E to F = 1 : 4, determine its vapour pressure, in terms of p
0
, at 298K.
3


Mole fraction of F =
4
4 + 1
=
4
5
or 0.8
From the graph,
vapour pressure of the mixture = 1.8 p
0

OR BY CALCULATION
P
E
= 0.2p
0
P
F
= 0.8 (2p
0
) = 1.6p
0

∴ vapour pressure of mixture = P
E
+ P
F
= 0.2p
0
+ 1.6p
0
= 1.8p
0



95 2A 1 c i
1c Two miscible liquids A and B form ideal solutions upon mixing. The boiling point of A is higher than that of B.
i Draw the boiling point-composition graph at 1 atm for mixtures of A and B and label the graph in detail. 3
Boiling point-composition curve

1 mark for labelling the x- and y-axis1 mark for the liquid curve
1 mark for the vapour curve
(deduct 1 mark if T
B
> T
A
)

C This question was well answered except that some candidates mistook the boiling point-composition diagram as
the vapour pressure-composition diagram


96 2A 2 c i
2c i Two miscible liquids A and B form ideal solutions when mixed. At 298 K, the vapour pressures of pure A and
pure B are 32 kPa and 16 kPa respectively. For a mixture of 1 mol of A and 3 mol of B at 298 K, calculate
(1) the vapour pressure of the mixture;
(2) the mole fraction of A in the vapour which is in equilibrium with the mixture.
4

(1) Vapour Pressure =
1
4
× 32 + 4 × 16 1 + 1 marks
= 20 kPa 1 mark
(Deduct ½ mark for wrong / no unit)

(2) Mole fraction of A =
8
20
=
2
5
1 mark
(Deduct ½ mark for including a unit in the answer.)


99 2A 2 a i ii
Phase Equilibria Unit 2 Page 8
2a A liquid mixture consists of 70.0 mol % of methanol and 30.0 mol% of ethanol. Suppose that the mixture is an
ideal solution. Calculate, at 298 K,
(At 298 K, the vapour pressures of methanol and ethanol are 12.5 kPa and 9.9 kPa respectively.)

i the vapour pressure of the mixture, and
ii the concentration of methanol, in mol%, in the vapour phase at equilibrium. (3 marks)

Phase Equilibria Unit 3 Page 1
Topic Phase Equilibria Unit 3

Reference
Reading

7.2.2–7.2.3
A-Level Chemistry Syllabus for Secondary School (1995), Curriculum Development Council, 203–204
Assignment
Reading

Advanced Practical Chemistry, John Murray (Publisher) Ltd., 78–80
A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 186–187

Syllabus
Non-ideal system
Deviation from Raoult's law
Enthalpy change of mixing

Notes
B. Non-ideal system

However, most solutions do not behave ideally. Some of them will give a (saturated) vapour pressure higher
than the expected and some of them will give a lower value.

1. Deviation from Raoult's law

This can be interpreted as the change in the strength of intermolecular forces.

Positive deviation
If the intermolecular forces among the two kinds of
particles (ALB) is weaker the original forces in
pure components (ALA & BLB), it will be easier
for the particles to escape from the liquid mixture
and give a (saturated) vapour pressure higher than
the expected at a given temperature.

This is called positive deviation from Raoult's law.

For an ideal solution, the liquid composition curve
is linear in shape.

If the solution is slightly positively deviated, the
curve will curve up a little bit. If the solution is
highly deviated, a curve with a maximium point
will result. This means that the mixture with that
particular composition is even more volatile than
either component.


Slightly deviated

Highly deviated


Negative deviation
Similarly if the intermolecular forces among the
two kinds of particles (ALB) is stronger, it will
give a (saturated) vapour pressure lower than the
expected at a given temperature.

This is called negative deviation from Raoult's law.

The minimium vapour pressure in the liquid
composition curve represents a mixture which is
less volatile than either component.


Slightly deviated

Highly deviated

Phase Equilibria Unit 3 Page 2

a) Positive deviation


A mixture of ethanol and benzene is a positive
deviation from Raoult's law.

It is a largely deviated system. The mixture has a
minimium boiling point at 0.55 mole fraction of
ethanol. At this point, both liquid and vapour have
the same composition. This mixture is known as
azeotropic mixture or azeotrope.

Azeotropic mixture is a constant boiling mixture
and cannot be separated by fractional distillation.

If a 0.20 mole fraction of ethanol is distilled, the
first distillate will contain 0.39 mole fraction of
ethanol. If the distillate is distilled continuously,
eventually, only a 0.55 mole fraction of ethanol
distillate will be obtained.

Boiling point-composition curve for ethanol /
benzene







Ethanol and water is another example of highly
positive deviation.

Fractional distillation can only purify the mixture
up to 0.94 mole fraction ethanol or 97% by mass of
ethanol. The remaining 3% water can only be
removed by drying agent e.g. calcium oxide
followed by distillation.

This explains why absolute ethanol is much more
expensive than 97% ethanol.



Boiling point-composition curve for ethanol / water
Phase Equilibria Unit 3 Page 3


b) Negative deviation


Trichloromethane and propane is a system of
highly negative deviation.

The mixture has a maximium boiling point at 0.65
mole fraction of trichloromethane.

If a 0.30 mole fraction of trichloromethane is
distilled, the vapour will contain less
trichloromethane (0.20 mole fraction) and more
propanone. And the liquid remain in the flask will
contain more trichloromethane.

Eventually, a constant boiling mixture of 0.65 mole
fraction of trichloromethane will be left in the flask
and cannot be separated into trichloromethane and
propanone. The distillate obtained will be pure
propanone.

Boiling point-composition curve for
trichloromethane / propanone


Similar if a 0.80 mole fraction of trichloromethane is distilled, the solution remain in the flask will be 0.65
mole fraction of trichloromethane. But the distillate obtained will be pure trichloromethane.






Hydrochloric acid is also a highly negative
deviation from Rauolt's law. Its azeotropic mixture
has a composition of 0.11 mole fraction of HCl.




Boiling point-composition curve for hydrogen
chloride / water
Phase Equilibria Unit 3 Page 4


c. Enthalpy change of mixing

The change in strength of intermolecular forces can further be confirmed by the enthalpy change of mixing of
components.

When the components of a ideal system is mixed, the temperature change is almost zero. This means no
special intermolecular attractions are formed or broken.

When the components of a system showing positive deviation is mixed, the temperature decreases. This means
that some intermolecular attractions are weakened. (i.e. bond breaking is an endothermic process.)

When the components of a system showing negative deviation is mixed, the temperature increases. This means
that some intermolecular attractions are strengthened. (i.e. bond formation is an exothermic process.)

Glossary
non-ideal system / solution positive deviation from Raoult's law negative deviation from Raoult's law
azeotropic mixture / azeotrope / constant boiling mixture enthalpy change of mixing

Past Paper
Question
92 1A 2 f i ii iii
93 2A 1 b
94 2A 2 c i ii
95 2A 1 c i ii
96 2A 2 c ii
97 2A 1 c
99 2A 2 b i ii

92 1A 2 f i ii iii
2f The vapor pressure versus mole fraction diagram for a two component system (A and B) is shown below:


i State the reason(s) which give(s) rise to the shapes of the curves in the diagram. 2
The attractive forces between A and B are weaker than those between molecules of the same kind. 1 mark
As a result, there is an increased tendency to escape form solution and that the vapour pressure of each of the
components is greater than that predicted by Raoult’s law. 1 mark

ii What do points P and Q represent? 1
P, Q are the vapour pressure of pure A and pure B respectively. 1 mark
iii What assumption(s) would have to be met for the curves to be linear? Give an equation to represent this
behaviour.
1
The intermolecular attraction between molecule A and molecule B is similar to that between molecule A and
molecule A and that between molecule B and molecule B. ½ mark
Ideal behaviour (Obeys Raoult’s Law)
P=X
A
P
A
º+X
B
P
B
º OR P
A
=X
A
P
A
º ½ mark

C iii Some candidates confused ideal gas law with Raoult's Law for ideal solution.

Phase Equilibria Unit 3 Page 5
93 2A 1 b
1b Draw vapour pressure versus composition graphs of two types of non-ideal solutions formed by mixing two
miscible liquids. Interpret these graphs in terms of intermolecular attractions.
4
Vapour pressure – composition diagrams for negative and positive deviations from Rauolt’s Law are :
(no dotted line -½)
If the attraction between the molecules A & B is weaker (stronger) than the average intermolecular attraction in
pure A & B, positive (negative) deviation results.
Weaker (stronger) intermolecular attraction means molecules have greater (smaller) chance to escape, hence
vapour pressure of the system is higher (lower) than that expected by Raoult’s Law.

C Many ca`ndidates were not aware of the relation between intermolecular interactions and non-ideal behaviour of
real solutions.


94 2A 2 c ii
2c Two miscible liquids E and F form ideal solutions on mixing. At 298 K, the vapour pressure E is p
0
while that of
pure F is 2p
0
.

i Sketch a graph of vapour pressure versus mole fraction for the above solutions at 298K. For a mixture of E and F
with mole ration E to F = 1 : 4, determine its vapour pressure, in terms of p
0
, at 298K.
3


Mole fraction of F =
4
4 + 1
=
4
5
or 0.8
From the graph,
vapour pressure of the mixture = 1.8 p
0

OR BY CALCULATION
P
E
= 0.2p
0
P
F
= 0.8 (2p
0
) = 1.6p
0

∴ vapour pressure of mixture = P
E
+ P
F
= 0.2p
0
+ 1.6p
0
= 1.8p
0


ii If E and F do not form ideal solution on mixing, in what possible ways could the vapour pressure of the above
mixture deviate from the value determined in (i)? Account for the deviation(s).
3
If deviation is negative, P < 1.8p
0
½ mark
If deviation is positive, P > 1.8p
0
½ mark
In case of negative (positive) deviation, the interaction betwee E and F is stronger (weaker) than the average of
interaction between E and E and between F and F. The molecules has a smaller (greater) chance to escape, thus
resulting in a lower (higher) vapour pressure. 2 marks
[Max. 2 marks, if only one of the cases is discussed.]


Phase Equilibria Unit 3 Page 6
95 2A 1 c i ii
1c Two miscible liquids A and B form ideal solutions upon mixing. The boiling point of A is higher than that of B.
i Draw the boiling point-composition graph at 1 atm for mixtures of A and B and label the graph in detail. 3
Boiling point-composition curve

1 mark for labelling the x- and y-axis
1 mark for the liquid curve
1 mark for the vapour curve
(deduct 1 mark if T
B
> T
A
)

ii Using your graph, explain how liquid B can be separated from a mixture containing A and B, by fractional
distillation.
4
If a solution with composition X
1
is heated to T
1
, the gaseous phase in equilibrium with it has the composition X
2

which is richer in B.
(1 marks for explanation; 1 mark for indication on the graph)
This vapour is cooled to T
2
and condenses to liquid with a composition of X
2
. Vaporization of this liquid leads to
a new vapour with a composition X
3
, which is richer in B than that with a composition X
2
and finally pure B is
obtained.
(1 mark for explanation; 1 mark for indication on the graph)

C This question was well answered except that some candidates mistook the boiling point-composition diagram as
the vapour pressure-composition diagram


96 2A 2 c ii
2c ii Predict whether the following pairs of liquids when mixed, would give solutions showing positive deviation
or negative deviation from Raoult's Law. Explain your prediction.
(1)
CH
3
CH
2
OH
and
CH
3

(2)
C
2
H
5
OC
2
H
5 and
CHCl
3
4
(1) Mixtures of ethanol and methylbenzene will show positive deviation from Raoult's Law. ½ mark
In pure EtOH, the intermolecular attraction is H-bond. ½ mark
In the mixture EtOH molecules are surrounded by methylbenzene, the attraction between the molecules is
mainly van der Waals' force. ½ mark
Weakening of the intermolecular force causes an increase in vapour pressure / escaping tendency of molecule.
½ mark

(2) Mixtures of C
2
H
5
OC
2
H
5
and CHCl
3
will show negative deviation from Raoult's Law. ½ mark
In the pure, liquids the intermolecular attraction is dipole-dipole interaction. ½ mark
In the mixture C
2
H
5
OC
2
H
5
forms H-bond with CHCl
3
Thus, the mixture will have a lower vapour pressure
than the pure liquids. ½ mark


97 2A 1 c
1c Three types of boiling point - composition curves for two miscible liquids A and B at one atmosphere pressure are
shown below.
7
Phase Equilibria Unit 3 Page 7

Account for the characteristics of these curves.

99 2A 2 b i ii
2b i At 1 atm pressure, the boiling points of pure nitric(V) acid and water are 359 K and 373 K respectively. At this
pressure, nitric(V) acid and water form an azeotrope which boils at 394 K. The azeotrope consists of 35.3 mol
%of HNO
3
,
Sketch a labelled phase diagram for the nitric(V) acid-water system at 1 atm pressure showing
(I) the boiling point - liquid composition relationship, and
(II) the boiling point - vapour composition relationship.

ii Describe all changes in the fractional distillation of an aqueous solution of 20 mol % of HNO
3
. (5 marks)

Phase Equilibria Unit 4 Page 1
Topic Phase Equilibria Unit 4

Reference
Reading

7.2.4
Chemistry (Structure and Dynamics), McGraw-Hill, 331–334

Assignment
Reading

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd.,187–189

Syllabus
Elevation of boiling point and depression of freezing point by an involatile solute
Boiling point of two immiscible liquids
Steam distillation

Notes
2. Elevation of boiling point by an involatile solute

A volatile solvent (A) has weak intermolecular forces among
the solvent particles (ALA).
A solute (B) is involatile only if the intermolecular forces
among the particles (BLB) are strong.

If an involatile solute (B) is soluble in the volatile solvent (A),
the forces among the solute and solvent particles (ALB) must
be stronger than the solvent-solvent interaction (ALA) and
solute-solute interaction (BLB). Otherwise, the solute will not
be soluble.




Since the solute-solvent interaction is the strongest, when an involatile solute is dissolved in a volatile solvent,
this must be a negative deviation from Rauolt's law. The vapour pressure of the mixture will be lower than the
pure solvent at any temperature.



Recall the phase diagram of pure water, pure water
boils at 100 ºC and freezes at 0 ºC.


If salt is dissolved in water, a higher temperature
will be required to rise the vapour pressure of the
mixture to atmospheric pressure. Therefore, the
presence of involatile solute increases the boiling
point of the solvent.


For example, curve AB shows the vapour pressure of pure water at different temperature. Normally, its vapour
pressure will reach atmospheric pressure at 100 ºC.

Curve CD is the vapour pressure of the aqueous salt solution. At any particular temperature, the vapour
pressure is always lower than that of pure water. And a higher temperature is required to make the solution
boil.
Phase Equilibria Unit 4 Page 2


If the lowering of vapour pressure is extended to
the lower temperature range, the vaporization curve
will meet the sublimation curve at a lower
temperature.

This will lead to a lower triple point temperature as
well as a lower melting point.

For this result, salt is sprayed onto the icy road to
melt the ice in winter.


The degree of elevation of boiling point and
depression of freezing point depends on the nature
of the solvent and the concentration of the solute.

(Surprisingly, it is not depending on the nature of
the solute.)






3. Boiling point of a mixture of two immiscible liquids

For a two components system, if the intermolecular forces between the two components (ALB) are very small
comparing with the original forces (ALA & BLB), the two liquids will be immiscible with each other.
This is an extremely case of positive deviation from Rauolt's law.


Under this circumstance, the two components will
vaporize independently, the vapour pressure will be
the sum of the vapour pressures of the two pure
components and independent of the mole fraction
of individual component.

P
T
= P
A
º + P
B
º

Comparing with an ideal solution :
P
T
= X
A
P
A
º + X
B
P
B
º

Since the total vapour pressure will be higher than
the vapour pressure of either component at any
temperature, the boiling point of the mixture will
also be lower than either component.

Nitrobenzene and water are two immiscible liquids.
Nitrobenzene and water have boiling points 211 ºC
and 100 ºC respectively. When they are mixed
together, independent of the relative abundance, the
mixture boils at 98 ºC.



Phase Equilibria Unit 4 Page 3


a) Steam distillation

According to the above principle, a heat sensitive organic compound can be separated by steam distillation.

Sometimes, ordinary distillation cannot be used to purify heat sensitive organic compound. This is because
some organic compounds decompose well before they boil. In order to separate them, the boiling point must
be lowered.

Most organic compounds are immiscible with water. Thus, water can be added to lower the boiling point of the
compound.

This is done by passing steam through the organic mixture to be separated or heat the mixture in the presence
of large amount of water. Steam provides both the heat and water for the distillation. The method is called
steam distillation.


Steam distillation

Since water and the organic compound are immiscible, water in the distillate can be separated by a separating
funnel.

Glossary
elevation of boiling point vaporization curve sublimation curve triple point temperature
depression of freezing point immiscible liquids steam distillation steam generator safety tube
separating funnel

Phase Equilibria Unit 4 Page 4

Past Paper
Question
92 2A 2c ii

92 2A 2 c ii
2c ii The total vapour pressure exhibited by a mixture of immiscible liquids is equal to the sum of their individual
saturated vapour pressures.
(I) Explain why steam distillation enables some heat-sensitive organic compounds to be distilled at a lower
temperature than their normal boiling points.
(II) A mixture of two immiscible liquids F and G boils at 98°C. At this temperature, the vapour pressures of F
and G are 733 mmHg and 27 mmHg respectively. Calculate the percentage of G by mass in the vapour when
the mixture boils.
(The relative molecular masses of F and G are 18.0 and 123.0 respectively.)
4
(I) A liquid boils when its vapour pressure reaches the value exerted by external pressure. Thus the total vapour
pressure exerted by an immiscible mixture of liquids will reach atmospheric pressure at a temperature below
the boiling-point of the heat sensitive / most volatile constituent. 1 mark
(II) P
F
= vapour pressure of F = 733 torr
P
G
= vapour pressure of G = 27 torr
Since the no. of mole of F is proportional to P
F
.
Similarly, the no. of mole of E is proportional to P
G
as PV = nRT. 1 mark
Let m
F
and m
G
be the masses of F and G in the system

P
F
P
G
=
n
F
n
G
=
m
F
M
F
m
G
M
G


or
m
f
m
G
=
P
F
M
F
P
G
M
G
=
733 × 18.0
27 × 123.0
= 3.97 ⇒ m
f
= 3.97 m
G
1 mark

Percentage by mass of G =
m
G
m
f
+ m
G
=
m
G
3.97 m
G
+ m
G
=
m
G
4.97 m
G
= 0.201 or 20.1% 1 mark

C ii To answer the questions, candidates had to realize that in the vapour phase, the number of moles of F and G are
proportional to their vapour pressures and then the candidates needed to set up the relationship
P
G
/ P
E
= n
G
/ n
E
= (m/M)
G
/ (m/M)
E



Phase Equilibria Unit 5 Page 1
Topic Phase Equilibria Unit 5

Reference
Reading

7.3


Assignment
Reading

A-Level Chemistry Syllabus for Secondary School (1995), Curriculum Development Council, 205–206
A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd.,189–193
Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 330–333
Syllabus
Three components system
Partition of a solute between two phase
Solvent extraction
Paper chromatography

Notes
III. Three components system

The three components systems that we are going to study consist of 1 solute and 2 solvents.

A. Partition of a solute between two phases


When a solute is added into a mixture of two immiscible solvents, it dissolves in both of
them. At equilibrium, the speed of diffusion from one solvent to another is the same as the
reverse speed. Therefore, the concentrations of the solute in both solvents will remain
constant.

Solute in lower layer d Solute in upper layer

And the equilibrium constant of the system is known as partition coefficient or distribution
coefficient, K
d
.

By convention, the concentration of solute in the less dense solvent (upper layer) will be
used as the numerator in the equilibrium law.
N.B. CCl
4
and CHCl
3
are the only two common organic solvents denser than
water.

K
d
=
concentration in the upper layer
concentration in the lower layer
or
[Solute
(upper layer)
]
[Solute
(lower layer)
]


K
d
can also be expressed as

[Solute
(upper layer)
]
[Solute
(lower layer)
]
×
molar mass of the solute
molar mass of the solute
=
conc
n
in gram per dm
3
in the upper layer
conc
n
in gram per dm
3
in the lower layer



Since the numerator and denominator always have the same dimension, K
d
always has no unit. The
concentration can be expressed in molarity, gcm
-3
or gdm
-3
, the choice of unit has no effect on the value of K
d
.



Phase Equilibria Unit 5 Page 2


1. Solvent extraction

Solvent extraction is an useful technique in organic chemistry. It allows partial removal of solute from one
solvent into another immiscible one. This is done by shaking the sample to be purified with an immiscible
solvent in a separating funnel.

Ether is a slightly polar organic solvent lighter than water. It is commonly used in solvent extraction because it
is immiscible with water and volatile. Once the solute is extracted, ether can be evaporated at reduced pressure
to obtain the pure sample.

N.B. Ether can never be evaporated by a naked flame because it is highly immflammable. High
temperature is also undesirable because ether forms explosive peroxide with oxygen at high
temperature.


a) Calculation

Example 1

At 291 K, the partition coefficient of butanoic acid, CH
3
CH
2
CH
2
COOH between ether and water is 3.5.
Calculate the mass of butanoic acid extracted by shaking 100 cm
3
of water containing 10 g of butanoic acid
with 100 cm
3
of ether.

K
d
=
[Solute
(ethereal phase)
]
[Solute
(aqueous phase)
]
= 3.5

Let x g be the mass of acid extracted by 100 cm
3
of ether.

x / 100
(10 - x) / 100
= 3.5 x = 7.78

Therefore, 7.78 g of butanoic acid will be extracted.


Example 2

For the same aqueous solution of butanoic acid, calculate the mass of butanoic acid extracted if two portions of
50 cm
3
ether are used.

Let x
1
g and x
2
g be the masses of acid extracted in the two portions.

In the first extraction,

x
1
/ 50
(10 - x
1
) / 100
= 3.5 x
1
= 6.36

In the second extraction,

The mass of acid remaining in the aqueous phase
= original mass - mass extracted in the first extraction
= (10 - 6.36) g = 3.64 g

x
2
/ 50
(3.64 - x
2
) / 100
= 3.5 x
2
= 2.32


The total mass extracted by the two 50 cm
3
portions of ether = 6.36 g + 2.32 g = 8.68 g

Although the same total amount of ether is used, the mass of acid extracted in two portions is larger. For this
reason, solvent extraction is usually done with a small amount of solvent at a time.


Phase Equilibria Unit 5 Page 3


2. Paper chromatography


Partition of a solute between two phases is not
limited to 2 immiscible liquids only. Paper
chromatography is also a kind of distribution
equilibrium. The solute partitions between the
stationary phase and the mobile phase.

K
d
=
[Solute
(moving phase)
]
[Solute
(stationary phase)
]


In paper chromatography, stationary phase is the
layer of water adsorbed on the natural cellulose
fibres of filter paper.
And, moving phase is the solvent used to carry the
solute along the paper.



In a mixture of dyes, different dyes have different partition coefficients between the moving phase and
stationary phase.
The dye with larger partition coefficient will move faster on the paper when the solvent is soaking up. Because
of these differences, different dyes can be separated.



a) R
f
value


The colour pattern obtained from paper chromatography is called paper
chromatogram. Each spot on the chromatogram is identified by a value
called R
f
value.

It is defined as : R
f
=
distance moved by the coloured spot
distance moved by the solvent front


R
f
is for a particular compound depends upon the solvent used and the
temperature. It always has a value smaller than 1. It is possible to
characterize a particular compound separated from a mixture by its R
f
value.



b) Separation of amino acids

A mixture of unknown amino acids can be separated and identified by means of paper chromatography.
However, all amino acid are colourless. They must be developed first. The positions of the amino acids in the
chromatogram can be detected by spraying with ninhydrin (a developer), which reacts with amino acids to
yield highly coloured products.

Glossary
three components system partition partition coefficient / distribution coefficient solvent extraction
separating funnel explosive peroxide paper chromatography stationary phase mobile phase
adsorbed R
f
value chromatogram characterize ninhydrin developer

Phase Equilibria Unit 5 Page 4

Past Paper
Question
92 2A 2 c i
96 1A 1 e i ii
98 2A 4 b i ii
99 1A 2 c i ii iii

92 2A 2 c i
2c i The distribution coefficient of a compound X between two immiscible liquids D and E is 12. X is more soluble in
D. What mass of X can be extracted form 50cm
3
of a solution of E which initially contains 4g of X when shaken
with 100cm
3
of D?
3
Let α g be the mass of X in 1 cm
3
of D and β g be the mass of X in 1 cm
3
of E
Since distribution coefficient is 12.
∴ α = 12β
and 100α + 50β = 4
100α +
50
12
α
= 4
α =
48
1250
= 0.0384
The mass of X in liquid D = 100α = 3.84 g 3 marks

C i Many candidates gave the mass of X remaining in E instead of the mass of X extracted from E. They probably did
not read the question carefully.


96 1A 1 e i ii
1e At 298 K, 50 cm
3
of a solution of I
2
in CCl
4
were mixed and shaken with 200 cm
3
of distilled water in a separating
funnel until equilibrium was attained. The two layers were then separated. 20.0 cm
3
of the CCl
4
layer required
12.15 cm
3
of 0.105 M S
2
O
3
2-
(aq)
for titration, whereas 50.0 cm
3
of the aqueous layer required 8.25 cm
3
of 0.0050 M
S
2
O
3
2-
(aq)
.

i Calculate the distribution coefficient of I
2
between water and CCl
4
at 298 K. 2

ratio of concentration of I
2
:
water
CCl
4
=
8.25 × 0.0050
50

12.15 × 0.105
20

1 mark
= 0.012934 = 0.013 1 mark
(Accept distribution coefficient expressed as [I
2
(CCl
4
)]/[I
2(aq)
], in which case the value calculated is 77.3 (77))
(Award ½ marks for a correct expression of K
d
)

ii If the 200 cm
3
of distilled water contain some dissolved KI, will this affect the value of the distribution
coefficient ? Briefly explain.
1
No change ½ mark
because distribution coefficient is a function of temperature only ½ mark
(Also accept K will change because there is a change in ionic strength/activity (1/0))


98 2A 4 b i ii
4b Even though the partition coefficient of ethanoic acid between water and 2-methylpropan-1-ol is 3.05 at 298 K, 2-
methylpropan-1-ol is still used to extract ethanoic acid from aqueous solutions.
Calculate the efficiency of ethanoic acid extraction (in terms of %) at 298 K by shaking 100 cm
3
of a 0.50 M
aqueous solution of ethanoic acid with

i 200 cm
3
of 2-methylpropan-1-ol;
ii two successive portions of 100 cm
3
of 2-methylpropan-1-ol.
Decide whether (i) or (ii) is the better extraction method. Explain your answer.

99 1A 2 c i iii
2c A mixture of amino acids, A, B and C, was separated by paper chromatography using an appropriate solvent. The
chromatogram obtained is shown below:

Phase Equilibria Unit 5 Page 5

(× is the starting point of the mixture)
i Briefly describe the principle underlying the separation of A, B and C by paper chromatography.
ii The amino acid spots are invisible to naked eyes. Suggest how to make them visible.
iii Calculate the R
f
value for A.

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