Negatively charged

fast moving particle

Atom is no longer unbreakable

Idea of atom introduced

No experimental evidence
Atom is the smallest unit of
matter and is not breakable
With experimental evidence
from the study of gas
Invention of cathode ray tube
Behaviour of cathode ray in
magnetic and electric field
Invention of the word "electron".
Raisin pudding model of atom
Gold foil scattering experiment
The idea of presence of tiny nucleus

Democritus

Dalton
Goldstein

Thomson

Rutherford
Chadwick

Study of radioactivity

Discovery of neutron
The idea of nucleus is breakable

Vaporization chamber
Ionization chamber
Accelerating plates
Construction

Mass of an atom

Radioactivity

Atomic Structure

Development of atomic
model

Mass spectrometer

Relative isotopic mass

Relative atomic mass

Relative molecular mass

Interpretation of mass
spectrum

Working principle - response to

m/e ratio

Vacuum Pump

Recorder

Detector

Deflecting magnetic field

To determine the ionization

energy of an atom
Determination of isotopic mass
Determination of atomic mass
Determination of molecular mass
Determination of molecular structure
The relative mass of a particular isotope in C-12 scale where
C-12 isotope is defined to have exactly 12 units of mass.

The weighted average of the relative isotopic masses for a particular

element in C-12 scale according to their natural abundance
The relative mass of a molecule where that the value is the
same as the sum of relative atomic mass of all atoms present
in the molecule.

1. Atomic Structure.mmap - 2005/5/23 -

History of discovery

Nature of radioactivity

Discovery of radioactivity

and

First order reaction

Independent of temp.

Nuclear bomb

Co-60 / Cs-137 (tumor)

I-131 (thyroid cancer)

P-32 (metabolism of plant)

I-131 (thyroid disease)

Geiger-Muller counter

Constant Half-life

Meaning of Half-life

re-orientation of the spinning

proton

Nature state of atoms after

the big bang / nucelus
formation

increasing of p:n ration

instablility of neutron when

isolated

lowering of p:n ratio

binding force between proton

and neutron

replusion among proton

100% speed of light

high energy EM wave

up to 99% speed of light

very fast moving electron

5% of speed of light

fast moving helium nuclei

Study the nature of

radiation

Extraction of radium and

polonium

Becquerel

Curie

Rutherford

particle

particle

radiation

particle

particle

radiation

Natural decay

Origin of radioactivity

Nuclear Reaction

Bio-tracer

Leak Detection

Artificial transmutation

Use of Radioactive isotope

Radiotherapy

Carbon-14 dating

Nuclear power

Molecular mass is numerically the

same as molar mass

Measurement of T

Measurement of m

Measurement of V

Measurement of P

Conditions a real gas behaves

virtually ideal

Assuming the vapor behaves ideally

Volatile liquid vaporizes easily by heating

No interaction among particles
Individual particle occupies no volume

interaction among particles is negligible

High temperature

Low pressure
Barometer in the laboratory

Increase in volume of
the gas syringe

Difference in mass of
the hypodermic syringe
before and after
injection

Thermometer
(final reading)

Definition of partial pressure - the pressure

of a component in the gaseous mixture if
that component occupies the same volume
by itself alone.

Principle

Setup of
apparatus

Operation

1/V

Charles' Law V
N

Boyle's Law P
Avogadro's Law V

Ideal gas Law

/ Equation
PV = nRT

Dalton's Law of partial

pressure

Determination
of molecular mass
of a volatile liquid

Total pressure of a gaseous

mixture is the same of the sum
of the partial pressure of all of
the component present

Take final reading when all readings are steady

Take all initial readings

Allow the system to reach a thermo-equilibrium

Precaution

Precaution

Precaution

particles are
far apart

particles are
moving fast

Insert the needle fully

into the gas syringe

Hold the end of the

syringe only

Hold the hypodermic

syringe horizontal

Take reading only when the

reading is steady

space occupied by individual particle is negligible

Some liquid may have

not vaporized
The vapor may be still
expanding
The liquid may leak out.
Volatile liquid usually
has low surface tension.
Body warmth may heat up
the liquid and expel it from
the syringe
Inject the liquid into the
deeper part, usually hotter,
of the gas syringe to
ensure better vaporization.

Take reading only when the

reading is steady

mole fraction (percentage by number)

The system may have not

reach thermo-equilibrium yet.

2. Mole Concept.mmap - 21/5/2005 -

Behaviour
of Ideal gas

How
much
is one
mole ?

Mole Concept

How many ?

How heavy ?

Definition

1st Law

2nd Law

1/n

1 F = 96500 C

Faraday constant

Avogadro's law

s.t.p.

r.t.p.

Carbon-12 Scale

Avogadro constant
(Experimental
measurement required)

Molar
mass

Molar volume

Molar
volume
of a gas

Faraday's
Laws
of
electrolysis

Relationship between
Current I, Amount of charge
Q and time t i.e Q=It

How large ?

Charges

Charges carried by
1 mole of electron

A solution with accurately known concentration

Process of determination of concentration of a
non-standard solution

criteria

A substance which can be used to prepare a

standard solution directly
known composition
stable composition
readily soluble
preferably with higher
molecular mass

strong acid vs strong base

strong acid vs weak base
weak acid vs strong base

Choice of
indicator

pH meter (titration curve)

thermometric titration

Standard solution

Standardization

Primary standard

Equivalence point

Titration

Acid-base
titration

Back titration

Redox titration

End point

Without indicator

Example

KMnO4 vs H2C2O4.2H2O

KMnO4 vs FeSO4

Iodometric titration

conductometric titration

Using indicator

The point when the end of titration is detected

The point at which the 2 reagents just react with

each other completely.

methyl orange or
phenolphthalein
methyl orange
phenolphthalein

methods for titration of

weak acid vs weak alkali
iodine / potassium iodide
starch solution
sodium thiosulphate
Determination of concentration of
chlorine bleach
Constant heating is required

Determination of percentage by mass of calcium

carbonate in chalk
Analysis of aspirin

Used if the reaction of direct titration is not instantaneous

/ if no suitable indicator for direct titration

3. Chemical Equations and Stoichiometry.mmap - 8/1/2005 -

Volumetric
Analysis

Formulae

Chemical Equations
and Stoichiometry

Formulae of
Compounds

Determination
of Formulae

Chemical Equations

Empirical formula

Molecular formula

Structural formula

Empirical formula

Molecular formula

Word Equation

Chemical Equation

Simplest whole number ratio

Actual no. of atoms

Connectivity of atoms

By Combustion Analysis

From Composition by mass

From empirical formula and

molecular mass

Water of crystallization

Stoichiometry

Volumes of gases

Reacting masses

Stoichiometric coefficients

Calculation based on equations

Electromagnetic Spectrum
Continuous Spectrum
Line Spectrum

Different models of
atom

The Electronic
Structure of Atoms

Background knowledge

4. The Electronic Structure of Atoms.mmap - 19/1/2005 -

Bohr's model

Setup of the apparatus

gas discharge tube

slit

prism or diffraction grating

Line spectrum

Continuum

Ionization of atom

Flame test

Red shift

Planck's equation

ground state

excited state

principal
quantum number

Identification of element at
remote star

Discovery of helium

Atomic emission spectroscopy

Unevenly spaced energy levels

Multiple transitions take place at the same time

Presence of numerous energy

levels (shells)

Process of excitation and

relaxation

Introduction of concept of
quantum

Convergence limits at the

higher frequency end of each
series

Unevenly spaced lines in each

series

Different series

Numerous lines

photographic film

Characteristic of the hydrogen

spectrum

Interpretation of the hydrogen

spectrum

Numerous lines

Unevenly spaced lines

Convergence limit
and continuum

As a mean of identification

Neon light with different

colours

Evidence of subshell

Evidence of shell

Uniqueness of atomic emission

spectra

Successive ionization energies

Definition

Atomic Emission spectrum of

hydrogen

Ionization energies

1st ionization energies across

periods

Electrons are orbiting around the nucleus in orbits with with different energy

The allowed energy of the electron in an atom is quantumized

Able to explain the emission spectrum of hydrogen spectrum but fail to explain the emission spectrum of those
multi-electron system.

Quantum numbers

Subsidiary (l)

Principal (n)

energy in multi-electron
system

shape of orbital / subshell

l = 0,1,2...(n-1)

shell no.

size

principal energy

n = 1,2,3 ...

By mathematical modeling

Heisenberg's uncertainty principle

Wave-particle duality of electron

Features of Bohr's model

Wave-mechanical model /
Orbital model

m = -l,...,0,...+l

spatial orientation of orbital

spin of electron

s = + or -

Magnetic (m)
Spin (s)

Nodal plane

Nodal surface

Radial probability distribution

Pauli Exclusion principle

Orbital / Electron cloud representation

repulsion with
the inner eusually stronger
repulsion with the
e- in the same shell
usually weaker

Gets more endothermic when

increase in attraction with e> increase in repulsion among
electrons, and vice versa
Value reflects the net
attraction between
the outermost electron
and the nucleus

Attraction with the nucleus

Relative
position of the
outermost e(Electronic
configuration of
the atom)
Repulsion
among
electrons

Energy required to
remove 1 mole of
electrons from 1
mole of gaseous
atom

Depending
on

General
pattern

Definition

Variation

Periodic Table

Atomic radius

Aufbau Principle

Electrons occupy the orbital with the lowest energy first

more evenly distributed electron cloud

full-filled 3d and half-filled 4s orbital

less repulsion

less repulsion

less repulsion

more evenly distributed electron cloud

no electron pair-up in 3d and 4s

half-filled 3d and 4s orbital

3d electrons shield 4s electron from the nucleus

and make 4s electrons more energetic

Electrons will occupy degenerate orbitals singly

with parallel spin before pairing up occurs.

Each orbital can accommodate

2 electrons with opposite spin

All electrons behave different in an atom i.e. no 2

electrons in an atom have the same set of quantum no.

Order of energy of different orbitals

Pauli exclusion principle

Copper

Completely filled quantum shell e.g. K, L, M

Noble gas cores e.g. [He], [Ne] etc.

Chromium

The difference gets even smaller when

3d orbitals are being filled up

Energy of 4s orbital is only a little

bit lower than that of 3d orbital

Hund's Rule (Rule of Maximum Multiplicity)

Irregularity
Exception

by notation
by electron in boxes
use of abbreviation

the p to e- ratio is increasing

the repulsion/shielding among electron is getting less

more difficult to remove electron from a positive particle

usually weaker

repulsion with the

e- in the same shell

usually stronger

repulsion with
the inner e-

the electronic configuration of an ion is the same as

the electron configuration of the preceding atom

the p to e- ratio is increasing

Proof of the presence of shells

the increases in successive ionization energies are too

large to be represented by linear scale

shift to the right

shift upwards

appear in tiers

In log scale

Successive ionization energy is always

much higher than its predecessor

Plot of Successive ionization

energies of an atom

Plot of successive ionization

energies of different atoms

including metallic radius

Nuclear charge

Primary
shielding
effect

Secondary
shielding
effect

the increase in primary shielding effect outweighs the

increase in nuclear charge

the increase in nuclear charge outweighs the increase in

secondary shielding effect.

Relative position of the

outermost e(Electronic configuration
of the atom)

Attraction with the nucleus

half of the distance between 2 chemically

bonded nuclei of the same element

Depending
on

Repulsion
among
electrons

contract across a period

expand down a group

half of the distance between 2 nuclei of the same element which

are not chemically bonded together in a crystal lattice

General trend

van der Waals' radius

Covalent radius

Variation of Successive
ionization energies

Representation of
electronic configuration

Building up of electronic
configuration on paper

Electronic
configurations and
the Periodic table

Variation of First
Ionization energy
across the first 20
elements

s-block, p-block, d-block and f-block elements

Showing 2-3-3
pattern across
period 2 and 3

Main trend

Effective nuclear
charge (nuclear
charge - shielding
effect)
experienced by
the outermost e-

Energy required to move the outermost electron to infinity

and escape from the attraction of the nucleus
Nuclear charge
Primary
shielding
effect
Secondary
shielding
effect

Getting less endothermic down

a group

Getting more endothermic

across a period

Position of the outermost e- (Size of atom)

the increase in nuclear charge
outweighs the increase in
secondary shielding effect
the increase in primary
shielding effect outweighs the
increase in nuclear charge
Imply presence of subshell

Unexpected drops
at O and S
(or peaks at N and P)

Unexpected drops
at B and Al
(or peaks at Be and Mg)

Imply pairing up of electrons in an orbital

Electron goes into a more
energetic p-subshell
(or full filled s-subsell in Be
and Mg - more evenly
distributed charges)
Electrons starts pairing up in O
and S - extra repulsion (or half
filled p-subshell in N and P more evenly distributed charges)

5. Electronic configurations and the Periodic table.mmap - 6/1/2005 -

Different forms of the same element /

compound in the same physical state
e.g. graphite and diamond,
ozone and diatomic oxygen

298K
1 atm

Standard conditions

pure, if it is a liquid or solid

Standard state

Experimental determination

Examples and definitions

Need of standard state and

condition

1M if it is an solution

most stable form at 298K, 1 atm

Presence of allotrope and

polymorph

Heat of Combustion

Heat of Formation

Heat of Solution

Heat of Neutralization

Enthalpy change as Heat flow (q) of a system at constant pressure returning

the system to the original temperature under a specific condition.
Formation of 1 mole of water
Neutralization of strong/weak acid / alkali
A solution with specific concentration /
an infinitely dilute solution is prepared.
1 mole of compound is formed from its constituent
elements in their standard states
Complete combustion of 1 mole of a specific
substance in excess oxygen

Heat of Hydration

bomb calorimetry to
determine the internal
energy change

Formation of 1 mole of hydrated crystal

from anhydrous solid
Experimental setup
conversion to enthalpy change
by calculation

simple calorimetry to
determine the enthaply
change

Philips Harris calorimeter to

determine heat of combustion

Common
assumptions

Experimental setup

Experimental setup
Polystyrene cup + cover
Insulating layer
thermometer
stirrer
Specific heat capacity of
solution is the same as that of
water
The rate of heat loss is
uniform / No heat loss to the
surrounding.
The heat capacity of some
components in the system can
be ignored.
The specific heat capacities of
some components are only
approximation.
Heat evolved will be the same
as heat flow in the original
definition of enthalpy change

6. Energetics.mmap - 17/1/2005 -

Standard enthalpy
changes

Significance

Enthalpy
and
Internal
energy

Definition : heat change of a system at constant

volume

Definition : heat change of a system at constant pressure

The link between the microscopic interaction among

particles and macroscopic observable change.

Enthalpy change

Internal energy change

Enthalpy change = Internal energy change +

Work done on the atmosphere

Heat flows out of the system because of the

increase in temperature of the system

Potential energy among the particles is converted

to heat energy when there is an overall
strengthening of attractions among the particles.

Bond formation > Bond breaking

Heat flows into the system as the temperature

of the system decreases

Heat energy is converted to potential energy

when there is an overall weakening of attractions
among the particles.

Bond formation < Bond breaking

Energy cannot be created or

destroyed

Some changes has no direct reaction at all

The direct reaction may be too vigorous

and too dangerous to be carried out

The extent (% of conversion) of

reaction cannot be controlled.

Formation of side products

Balanced equation according to definitions

Calculation involving heat capacity

Calculation of mole

Unit, usually in kJmol-1 must

be included

+ and - sign must be included

3. Constituent atoms

2. Combustion products

1. Constituent elements

Patience and careful manipulation

Some common references in

constructing energy cycles

Prerequisite

Need of Hess's Law

Born-Haber cycle as energy cycle used

to determine the heat of formation

Energy cycle & energy level diagram

Another version of law of

conservation of energy

The total enthalpy change of a chemical reaction is independent

of the route by which the reaction takes place

Endothermic
process

Exothermic
process

Relationship between Enthalpy

change and Internal energy
change

Exothermic and
Endothermic process

Energetics

Hess's Law

Calculation

unit and sign of the answer

Attraction among oppositely

charged ions
Repulsion among similarly
charged ions

Some terms

Different
arrangements
of lattice points

Balance between
non-directional
electrostatic attraction
and repulsion

face centered cubic

(f.c.c.) structure
simple cubic structure
Actual arrangement is
depending on

ionic radius

Lattice point

Unit Cell

Coordination number (C.N.) no. of nearest neighbour

e.g. NaCl

Potential well diagram

C.N. = 6 for both ions

C.N. = 8 for both ions
e.g. CsCl

Stoichiometry of the
compound
ionic radius ratio
Determination of empirical
formula
1. the smallest unit containing
all the fundamentals of a crystal
without repetition.
Definition

Determination of no. of
different ions in an unit cell

2. the smallest unit of a crystal

from which the original crystal
structure can be recreated by
repetition in 3-dimensional space.
Determination of
empirical formula
The position of a formula unit
of the compound considered.
Definition - Distance from the centre of an ion to
the point of zero electron density between 2
adjacent ions.

Size of
isoelectronic
ion

Value
depending on

determined by X-ray
diffraction

p to e- ratio

no. of atoms
present

Electron density map

polyatomic ion
is bigger than
simple ion
In general, negative
ion is bigger than
positive ion

As the no. of electrons and

electronic configurations are the
same, the size is only depending
on the number of protons present.

7. Ionic bonding.mmap - 19/1/2005 -

Energetics
of
formation

Ionic Bonding

Ionic
crystals

Born Haber Cycle

Stoichiometry
of
ionic
compounds

Heat of formation

always positive

Removal of 1 mole of electrons

from 1 mole of gaseous atoms
/ ions

always positive

formation of 1 mole of gaseous

atoms

formation of 1 mole of compound

Atomization energy of element

Ionization enthalpy of atom

Addition of 1 mole of electrons

to 1 mole of gaseous atoms /
ions

negative : attraction between the incoming

electron and the nucleus > the repulsion between
the incoming electron and the existing electrons

depending on the packing

efficiency i.e. crystal
arrangement

depending on charge density

of ions involved

positive : attraction between the incoming

electron and the nucleus < the repulsion
between the incoming electron and the existing
electrons

always negative

Formation of 1 mole of ionic

compound from its constituent
gaseous ions

Electron Affinity of atom

Lattice energy

Construction of Born
Haber Cycle for the
hypothetical ionic
compounds
e.g. MgCl and MgCl3

Cations and anions are just in

contact with each other

All ions are perfect spheres

The lattice
arrangement of the
hypothetical compound
is known

Hypothetical lattice energy

calculated from the ionic model

Construction of Born Harber cycle for

the naturally occurring ionic
compound e.g MgCl2

Indeed, the stability of an ionic compound is mainly

arising from the formation of ionic bond among
oppositely charged ions.

Positive metal ion + free electron are actually more

energetic (less stable) than a gaseous metal atom

a measure of strength of ionic

bond

Limitation of using stable

electronic configuration to
explain

Nature prefers the

stoichiometry with
the most exothermic
heat of formation
i.e. highest stability
comparing with the
constituent elements

Assumptions
of
ionic
model

The bond is purely ionic

The value of heat of formation is mainly determined

by the values of ionization energies and lattice energy

Strength of Covalent
bond

Attraction between nucleus,

bonding electron and another
nucleus

Replusion among the electrons

directional attraction

e.g. BF3

Expansion of octet

Can be less
than octet

Period 2 elements never

excess octet

Formation of
more bonds

More overall
exothermic change

High overall stability

e.g. PCl5, SO42-

Availability of low lying energy

orbital (e.g. 3d orbital
comparing with 3p orbital)

an electron acceptor with a

vacant p-orbital for dative
bond formation

Energetically unfavorable

3s orbital has much higher

energy than 2p orbital

# of p - # of e- associated with
an atom assuming that all
bonding e- are belonging to
the more electronegative atom

# of p - # of e- associated with
an atom assuming that bonding
e- are equally shared

e.g. NH4+, H3O+ NH3BF3, Al2Cl6

Overlapping of a lone pair with

a vacant orbital

a covalent bond in which the

bonding electrons are supplied
by one atom only

Promotion of paired electrons

to low lying energy orbital
(e.g. 2p comparing with 2s, 3d
comparing with 3p) to yield
more unpaired electrons for
bond formation

Increase in electron density

along the inter-nuclear axis

Constructive interference of
atomic orbitals

Replusion between the nuclei

Potential well diagram

Cases not obeying

octet rule

Cases obeying
octet rule

Oxidation number

Formal charge

Dative covalent bond

Pairing up of
unpaired electrons
(bonding electrons)

Overlapping of atomic orbital

Balance between
electrostatic attraction
and repulsion

Formation of
covalent bond

Drawing of Lewis
structure

Covalent bonding

Giant Covalent Structure

Shape of molecules and

polyatomic ions

Factors affecting bond

strength

(Average) Bond
enthalpy/energy E(X-Y)

Bond Dissociation Energy

D(X-Y)

In the range of 150-1000 kJmol-1

Energy required to break a particular bond
The average energy required to break a type of bond
Estimation using enthalpy change of atomization

Bond length

Bond order

Using bond energy to estimate the enthalpy change of a reaction

no. of bonding electrons / 2

Estimation of bond length

Breakup of additivity of
covalent radius

Atomic size
(covalent radius)

(Primary) shielding effect affects the nuclear

attraction experienced by the bonding electrons

The longer the bond length, the weaker will be the

bond

Resonance

Polarity of bond
covalent bond with certain ionic character is found to be
stronger than purely covalent or purely ionic bond
bond polarity

Description of shapes

Valence shell electron pair

repulsion theory

repulsion among the lone pairs

on adjacent atoms

Electrostatic repulsion is very

sensitive to distance

Electrons centres tend to

separate from each other as
far as possible to minimize
mutual repulsion

Electron centres : lone pair,

single bond, double bond,
triple bond

e.g. weak F-F, O-O and N-N

bond

repulsion between lone

pair-lone pair > lone pair-bond
pair > bond pair-bond pair
lone pair always occupies
equatorial position in a five
electron centres system
linear, angular (V-shaped or bent), trigonal planar, tetrahedral, trigonal
pyramidal, trigonal bipyramidal, seesaw, T-shaped, octehedral, square
planar
In the describing of the shape of molecule, the presence of lone pair is
not included.

Diamond

Graphite

Quartz (SiO2)

tetrahedrally arranged
strong C-C single bond only
high hardness, high melting point, electrical insulator, excellent heat conductor
arrange in hexagonal layers
strong C-C bond, bond order 1 1/3, within layer
weak van der Waals force between layers

high hardness, high melting point

low hardness, very high melting point, conducting along the layer, slippery
between layers

8. Covalent bonding.mmap - 2005/5/21 -

e.g. Cl2

e.g. HCl

The bond is
non-polar

Polar
covalent
bond

Pure covalent bond

Polarity
of a
molecule

(Permanent)
Dipole
moment

The bonding electrons

are not shared equally

The bonding electrons

are shared equally

atoms have different

electronegativity

Definition - product of quantity of charge (q)

and distance of charge separation (d)
The dipole moment along a bond is pointing from
the less electronegativity atom to the more
electronegativity atom
Lone pair

Depending on the vector

sum of all dipole
moments

Contribute a dipole moment

pointing away from the atom
Geometry of the molecule
magnitude of individual
dipole moment
A molecule with non-polar
bond only

Non-polar
molecule

Polar molecule (Dipole)

Do not /
weakly
attracted by
an electric
field

A molecule with all dipole

moments canceling out each
other
Non-polar molecules
are also attracted by
an electric field as a
weak temporary dipole
moment will be
induced onto them by
the electric field
A molecule with non-zero
net dipole moment
May not be able to tell the
actual direction of the net
dipole moment
Attracted by an electric field

9. Intermeidate type of bonding.mmap - 26/1/2005 -

Starting from
pure covalent
bond

Starting from
pure ionic bond

Intermediate Type of
Bonding

Assumptions
of simple
ionic
model

The lattice arrangement of the compound is known, if it is hypothetical

All ions are perfect spheres

Cations and anions are just in contact with each other

and clearly separated from each other

Polarization of
anion

Mutual repulsion
of electron cloud
in an ionic lattice

e.g. NaCl (almost purely ionic)

The ions are not

perfectly
spherical

Certain covalent
character

Polarization of
anion

p to e- ratio

secondary
shielding
effect

primary
shielding
effect

e.g. AgCl, AgBr, AgI, ZnS

Ions may not

clearly separated
from each other

ease of distortion of
electron cloud

inversely proportional
to the nuclear
attraction on the
electron cloud

electronic
configuration

shielding effect

nuclear charge

directly proportional to the

charge density of a cation

reflects the attraction on the

incoming electron to be added
to an atom

reflects the attraction on the

outermost electron in an atom

Depending on the effective

nuclear charge experienced by
the bonding electron

Not applicable to noble gases

Increase across a period and

up a group

Polarizing power of a cation

Polarizability
of an anion

Polarization - distortion of electron cloud

of anion under the influence of cation

A very different
value implies failure
of the ionic model with strong
covalent character

A more agreed value implies

a situation similar to the
assumptions of ionic model pure ionic bond

The bond is purely ionic. i.e. no sharing of electron or incomplete transfer of electron

The lattice energy

calculated based on
the ionic model is
never the same as
the experimental
value

Anion is always
polarized by
the cation

ionization energy

Tendency of an atom to
attract the bonding electron in
a stable molecule

For all real

ionic compounds

Electronegativity
Pauling's scale

electron affinity

Fluorine has the highest assigned value : 4.0

The percentage of ionic character of a covalent bond is depending on

the difference in electronegativity of the 2 elements bonded together

Nature of metallic bond

Sea of electrons model

lattice of positive ions

immersed in a sea of
delocalized electrons

Non-directional in nature

agitation of delocalized
electrons

delocalized electrons capable to reform the

metallic bond even if the positive ions are shifted

delocalized electrons get

excited and give out luster

Electrostatic attraction among positive

ions and sea of delocalized electrons

high ductility and

malleability

high conductivity

metallic radius = covalent radius

unique
properties of
metal

metallic luster

Charge density of the positive

ion e.g. Na+ > K+ > Rb+

abab... pattern

C.N. = 12

In molten state, most metallic

bond are not broken

high charge density of the positive ion limited the

availability of the valence electrons e.g. Hg

no. of valence electrons e.g.

Al > Mg > Na

In the range of 100-500 kJmol-1

Attraction on the delocalized
electrons

Availability of delocalized
electron
Big difference between m.p.
and b.p.

hexagonal close packing

(h.c.p.)

C.N. = 12

abcabc... pattern

C.N. = 8

(face centred) cubic close

packing (f.c.c. or c.c.p.)
tetrahedral holes and
octahedral holes
body centered cubic (b.c.c.)
Determination of no. of atoms
in an unit cell

open-structure (68%)

close-packed structure (74%)

Strength of metallic
bond

Metallic crystal (Giant

metallic structure)

Metallic bonding

10. Metallic bonding.mmap - 22/2/2005 -

2 per H2O molecule, 1 per HF,

NH3, MeOH molecule

H on F, O and N
Attraction between a
naked proton and a lone
pair

An exceptionally strong directional dipole-dipole interaction

hydrogen atom bonded onto a very
electronegative atom / entity

overall strength depends on

formed between molecules

(usually) gives higher b.p.

intermolecular

intramolecular
dimerization of carboxylic
acids in vapour state /
non-aqueous solvent

unique properties of water

formation of secondary
structure in protein and DNA

Examples

intermolecular and
intramolecular hydrogen
bond

Estimation of strength of hydrogen bond

Strength (1/10 of covalent bond)

5-50 kJmol-1

lone pair on a very electronegative atom

including H on CHCl3
lone pair on F, O and N only
difference in electronegatvitiy
average no. of hydrogen bond
per molecule

Hydrogen bonded molecule has higher boiling point that

ordinary polar molecule with comparable size.

Experimental

hydrogen bonded molecules also

possesses van der Waals' forces

H-bond breaking

H-bond formation

e.g. HF, H2O, NH3, MeOH comparing with other

molecules with comparable size

formation of new
intermolecular forces >
breaking of old intermolecular
forces

Period 2 hydrides comparing with hydrides of period 3 to 5

Mixing ethanol and hexane

Mixing trichoromethane and ethyl ethanoate

a substance would be soluble

(usually) gives higher solubility
in water

formed within a molecule

prevents the formation of intermolecular hydrogen bond

overall polarity of the molecule

(actually more important than
ability to form H-bond)

ability to form hydrogen bond with water

e.g. trans-butenedioic acid
e.g. alcohols
(usually) gives a lower b.p.
forming bond is better than
not forming bond

Low density of ice

highest density at 4 C

forming strong bond is better

than forming weak bond

open structure of ice

water expands upon freezing

diamond like structure

at 0 C

from below 0 C to 0 C
melting of ice

DNA

Protein

Variation of density with

temperature (K.E.)

double helical structure

single helical structure

from 4 C to 100 C

from 0 C to 4 C

rapid collapsing of open structure

thermal expansion of solid

structure

six membered rings of O linked

by O-HO linkage

density drops

density increases sharply

continuous collapsing
of open structure

thermal expansion of liquid water

still possesses certain hexagonal network

density increases continuously

density drops

cytosine - guanine pair

thymine - adenine pair

hydrogen bond between

heterocyclic bases on 2
separate strands

hydrogen bond between N-H and C=O group among different amide
groups along the polypeptide chain

3 H-bonds
2 H-bonds

11. Intermolecular Forces.mmap - 2005/5/23 -

Hydrogen bond

Intermolecular
Forces

Type of dipole (polar

molecule)

van der Waals forces

Molecular crystal

permanent dipole

permanent separation of centre of positive charge and centre of negative charge

no interaction (attraction and

repulsion) among particles

individual particle occupies no

volume

possessed by all kinds of molecules including polar molecules

the fluctuation of electron cloud creates

an instantaneous dipole

possessed by all polar molecules (dipoles)

instantaneous/temporary
dipole

induced by a permanent dipole

with instantaneous
dipole-induced dipole
interaction only

b - volume of individual particle

the opposite ends attracted

each other

dispersion force

London force

temporary dipole-temporary
dipole interaction

induced dipole-induced dipole

interaction

branched isomer
of hydrocarbon
has lower boiling
point

lower b.p. and m.p.

higher b.p. and m.p.

the opposite end of different

temporary dipoles attract each
other

stronger overall
strength for
molecules with
comparable size

weaker overall strength

for molecules with
comparable size

polarizability of constituent atoms

e.g. telfon/poly(tetrafluoroethene)

increases with increasing

molecular size / surface area
e.g butane vs 2-methylpropane

with dipole-dipole
interaction, dipole-induced
dipole interaction and
instantaneous
dipole-induced dipole
interaction

an instantaneous dipole induce

a temporary dipole on another
molecule

other names

a permanent dipole induce a

temporary dipole onto another
polar/non-polar molecule

also called permanent dipole

induced dipole interaction

attractions among opposite

ends of permanent dipole

also called permanent

dipole-permanent dipole
interaction

a - attraction among particles

assumption of
ideal gas law

van der Waals' constants

Real gas does

not obey ideal
gas law
perfectly

induced by instantaneous dipole

dipole-induced dipole
interaction

dipole-dipole interaction

Condensation of solid and liquid at low temp.

Real gas equation

induced dipole

Evidence

Origin

Polar
molecules

instantaneous dipole-induced
dipole interaction

Strength (1/10 of
covalent bond)
5-50 kJmol-1

Non-polar
molecules

depending on the
polarizability of
the molecule

half of the internuclear distance between 2 atoms

of the same element which are not chemically
bonded together in a crystal lattice

face-centred cubic structure

(f.c.c)

face-centred cubic structure

(f.c.c)

van der Waals' radius

iodine

dry ice

Simple molecular

Macromolecular

non-conducting

Giant metallic structure

Giant ionic structure

Giant covalent structure

Molecular structure

Structure and
properties of
materials

Giant structure

12. Structures and properties of materials.mmap - 2005/6/5 -

usually solid

In general, like dissolves like

the rigid structure transmits the

vibration of the C atoms efficiently

bonding electrons in most covalent bonds are not delocalized

intermolecular forces never stronger than covalent bond

solubility depending on the polarity of the solute and solvent

soft and weak

usually gases, liquids or low melting solids

fat and oil - marginal cases, with just over 100 atoms

e.g. H2O, NO2, S8, P4

under 100 atoms

weaker intermolecular forces

e.g. starch, protein, plastic

over thousands of atoms
stronger intermolecular forces
no delocalized electrons

insoluble in any solvent

high melting point

high density

hard

e.g. diamond, quartz, graphite

strong covalent bond

usually non-conductor of
electricity

Exception - diamond is an
excellent conductor of heat

presence of delocalized electrons along the hexagonal layers

weak van der Waals' forces between layers

flat hexagonal layers

weak van der Waals' forces between layers

usually poor conductor of heat

brittle
slippery
conducting

repulsion cleaves the crystal

weak van der Waals' forces

between layers

strong C-C bond, bond order 1 1/3

large space between layers

high melting, even higher than diamond

lower density than diamond

slight dislocation brings ions of similar charge together

only conducts in molten or aqueous state

increase in disorderness

dipole - ion interaction

the ions are not free to move in solid state

brittle

high density

hard

high m.p. and b.p.

Speical case : Graphite

strong ionic bond

presence of ions

hard

high m.p. and b.p.

If soluble, only soluble in aqueous solvent

sometime, strong metallic bond

high conductivity of heat and electricity

malleable and ductile

high density
Presence of sea of delocalized electrons
Soluble in mercury

Concentration of reactants
Pressure
Temperature
Surface Area
Catalyst
Light

Definition of Rate

Measuring of
Reaction Rate

Rate of Chemical
Reactions

Factors affecting
Reaction Rates

13. Rate of Chemical Reactions.mmap - 2005/6/5 -

Change in quantity per unit time

Quantity is usually expressed in moldm-3

Time is usually expressed in s

Depending on the units of quantity and time

Usually expressed in moldm-3s-1

Instantaneous rate

Average Rate

Unit of rate of reaction

Different rate
Initial Rate
(Instantaneous rate at t = 0)

Other possible units : mol, g

For gases : Pa, mmHg, atm,
cm3, dm3

by sudden cooling

by dilution with a large amount of water

by removing the catalyst

Need of a calibration curve

Transmittance and Absorbance

by removing one of the reactant

constant amount of Br2 produced / phenol consumed

starch indicator

constant amount of I2 produced / S2O32- consumed

phenolphthalein
indicator

constant amount of methanal reacted / HSO3- consumed

constant amount of S ppt.

produced to mask the cross

Measuring of mass of the

reaction mixture

Measuring of colour intensity

Measuring of volume of gas

Quenching of reaction before titration is done

Methanal Clock
experiment

Disproportionation of
Na2S2O3 in acidic medium

By measuring a physical quantity related to the

amount of a chemical

By titration

Differential form of rate equation / law

Constant time approach

(fix the time interval
and determine the
amount present)

Constant amount approach

(fix the amount to be
reacted and determine
the time required to
complete the reaction)
Iodine Clock
experiment
I- vs H2O2

Reaction
between Br- and
BrO3- in acidic
medium

methyl red
indicator

Differential form

Order with respect to individual reactant

Order of reaction

Rate constant k

Overall order of the reaction

Unit of rate constant is depending on the overall order of
the reaction
A value depending on temperature only
the rate is independent of the
concentration of the reactant

Ordinal form

Zeroth order
Different order with
respect to a reactant
First order

Second order

Usually occurring in catalyzed reaction

where the availability of the catalyst
surface is the limiting factor of the rate
the rate is directly proportional to the
concentration of the reactant
the rate is directly proportional to the
square of the concentration of the
reactant

Zeroth order reaction

Rate Equation / Law

half life

Rate Equations and

Order of Reactions

The concentration of C-14 in

atmosphere is assumed to be
constant
Integrated
form

First order
reaction

The percentage of C-14 in a living

organism is assumed to be constant.
half life

carbon-14
dating

By comparing the percentage/beta

emission of C-14 in an archaeological
sample and the percentage/beta emission
of C-14 in a new sample, the age of the
archaeological sample can be estimated.
The rate of decay is independent of
temperature as it doesn't involve collision
among particles

Second order reaction

half life

Initial Rate method

From the initial rate with different initial concentrations

If there is more than one reactant involved, keep the concentrations of all reactants
other than the one being studied virtually constant by keeping them in large excess
By plotting
concentration against
time

Determination of
rate equation / law

Horizontal line
By plotting
graph

By trial and
error

By plotting rate against

concentration

zeroth order

Straight inclined line

zeroth order

Straight inclined line

parabola

first order

second order

By plotting rate against [A] or [A]2 etc to see which will give
a straight inclined line passing through the origin
By plotting [A] or ln[A] or 1/[A] against time
Plotting log (rate) against log
(concentration)
14. Rate Equations and Order of Reactions.mmap - 2005/1/31 -

The slope will be the order of reaction with

respect to the reactant

The distribution is
temperature
dependent
The total area under the curve is independent of temperature.
i.e. the total no. of particles present

e.g iron in Harber process

By breaking up a single step into a multi-steps
reaction with lower activation energy
negative catalyst

positive catalyst

Providing an
alternative pathway
with a different
activation energy,
usually lower.

e.g. H+ in decomposition of H2O2

The catalyst has the same phase as the reactants and product

e.g.
acid-catalysed
esterification
The catalyst has a different phase as the reactants and product

Effect of catalyst

homogeneous
catalysis

Simple Collision
Theory (Effective
Collision)

(A)Arrhenius Constant

Energy larger than

activation energy
Arrhenius Equation

(Z) Collision
Frequency

Depending on the
nature of the reaction

Vary only a little when the temperature change

(P) Orientation / geometrical

/ probability factor

The step with the highest activation energy

The step with the lowest rate

can be isolated at low temperature

e.g. carbocation

e.g. a pentavalent transition

state

Repeat a reaction at two

different temperature
In the reaction k can be
replaced by rate if initial rate
method is used
k can be replaced by 1/t if constant
amount approach is adopted

An energy barrier the reactants need to overcome for the reaction to proceed.
By varying the temperature and measuring the rate of a reaction
A plot of ln k versus 1/T
A plot of ln rate versus 1/T if
initial rate method is used
A plot of ln 1/t versus 1/T if constant
amount approach is adopted

rate-determining step
(r.d.s.)

Reaction intermediate

can never be isolated

Determination of
activation energy

Multi-stage Reaction

Single stage reaction

transition state (or

activated complex)

Activation Energy

Energy profile

The Effect of
Temperature Change
and Catalyst on
Reaction Rate

Maxwell-Boltzmann
distribution of
molecular speeds

Catalysis

Other examples

heterogeneous
catalysis

Haber process

e.g. Catalytic
decomposition
of hydrogen
peroxide by
maganese(IV)
oxide
Fe(s)

Contact process
hydrogenation of oil

Enzymes

Catalytic Converter

Gasification of naphtha in product of town gas

Ni(s), Pt(s) or Pd(s)

Pt(s) or V2O5(s)

chemsorption / adsorption on the surface of the catalysis

Ni(s) and NiO

Rh(s) and Pt(s)

zymase in the fermentation by yeast

15. The Effect of Temperature Change and Catalyst on Reaction Rate.mmap - 21/5/2005 -

including all species

Excluding those species having no
effect on the equilibrium position e.g.
solvent(species in large excess),
insoluble solid/liquid
Examples

Equilibrium
constants

At equilibrium and only at equilibrium,

the order of reaction with respect to a
species will be the same as the
stochiometric coefficient of the species
Generic equilibrium constant, K
Equilibrium constant in terms
of concentration, Kc
Equilibrium constant in terms
of partial pressure, Kp

Significance of
equilibrium constant

Determination of
Equilibrium constant

Unit of equilibrium constant

Esterification

The equilibrium concentrations of all species are determined by the

initial concentrations of them and the equilibrium concentration of
any one of them.

Construction of a
calibration curve
using colorimeter
Formation of
[Fe(NCS)]2+(aq)
complex

Reaction between
Fe2+(aq) and Ag+(aq)

Assuming that the rate of reaction is extremely slow

and quenching is not required before any titration is
done.
Preparation of solutions with
known [Fe(NCS)]2+(aq)
concentration using excess
Fe3+(aq) or NCS-(aq)
Determination of the equilibrium concentration of
[Fe(NCS)]2+(aq) using colorimeter and the calibration
curve prepared
Assuming that the rate of reaction is extremely
slow and quenching is not required before any
titration is done
The titration is self-indicating if standard
KCNS(aq) is used in the determination of the
concentration of Ag+(aq). The solution will turn
red at the end point with the formation of
blood red [Fe(NCS)]2+(aq) complex.

The value is temperature

dependent.

The value is depending on the

relative stability of the
products comparing with the
reactants

The value shows the relative amounts of products and reactants when
the system is at equilibrium i.e. extent of reaction at equilibrium.

16. Dynamic Equilibrium.mmap - 6/4/2005 -

Equilibrium
Law

Equilibrium

Dynamic Equilibrium

Equilibrium
position

A state where no macroscopic

change is observed.

All chemical equilibria are

dynamic in nature. i.e.
forward rate = backward rate

The amounts of reactant and

product are usually not equal
in an equilibrium.

Examples

Thermal dissociation of
calcium carbonate

Esterification

Action of acid and alkali on

bromine water

Action of acid and alkaline on

potassium dichromate

Action of acid and alkali on

bismuth chloride

Definition : a set of reactant and product concentration

Using of equilibrium constant and reaction quotient

to predict the direction to which the equilibrium
position will be shifted.

Q = K : the system is at equilibrium

Q > K : the equilibrium position will be shifted to the left

Q < K : the equilibrium position will be shifted to the right

Effect of change
in pressure

this has no effect on

the equilibrium
position

The rate of a reaction

with a higher
activation energy is
more sensitive to the
change in
temperature

Catalyst does not change the relative stability of

the products comparing with the reactants

Catalyst has no effect on the equilibrium position.

It only shortens the time required for a system to
reach a state of equilibrium.

Use of change in
distribution of molecular
speed to explain the
effect of change in
temperature on the
equilibrium position.

by adding an inert gas

by adding one of the product/reactant

by decreasing/increasing the volume

Effect of change in concentration

The principle states that when a system in equilibrium is

subjected to a change, the system will response in a way so that
the effect of the change imposed will be minimized.

Reaction Quotient (Q)

Le Chatelier's
principle
Effect of
change in
temperature

Effect of catalyst

Ka1 is always much

larger than Ka2

Successive
ionization of
polyprotic
(polybasic) acid

A more negative pKa (pKb) value means a larger Ka (Kb)

value, thus a stronger acid (base).

HA- is relatively more stable

when comparing with H2A than
A2- when comparing with HAA2- has a much higher charge
density than HA- and has a very
high potential energy i.e. more
unstable
It is more difficult to remove a
positive proton from negative
HA-(aq) than from electrically
neutral H2A(aq)
Beside the small value of Ka2, the second step of the
ionization is also suppressed by the presence of H3O+ from
the first step of dissociation which will tend to shift the
equilibrium position of the second step to the left. This is
known as common ion effect (of H3O+ in this case).
Eventually, the amount of H3O+ from the second step of
ionization will be very minimal.
Determination of acidity constant Ka by half-way neutralization
The value of Ka is only depending on temperature but the % of dissociation of a
weak acid is depending on concentration as well.

17. Acid Base Equilibrium I.mmap - 6/4/2005 -

Acidity and
Basicity
constants

Different
definitions

Arrhenius definition
Bronsted Lowry
definition
Lewis defintion

acid : substance that produces

H+ in water

Introduction of the concept of

conjugate acid-base pair

base : substance that produces

OH- ions in water

acid : proton donor

base : proton acceptor

acid : electron acceptor

base : electron donor

An Arrhenius acid (base) must be a Bronsted Lowry acid (base) and a

Bronsted Lowry acid must be a Lewis acid (base) but not vice versa.

A neutral
solution
has a pH 7
only at
25C.

Water is a very poor conductor as it always possesses very small

amount of H3O+(aq) and OH-(aq) ions i.e. 1 pair of ions for every 556
million water molecules

Need of calibration using a

buffer solution before use

using pH paper / universal indicator

Every unit increase / decrease in pH scale means a ten-fold decrease / increase

in the concentration of hydroxonium (H3O+) ion

Originated from French "pouvoir hydrogene" (power of hydrogen).

Auto-ionization
(dissociation) of
water

Acid Base
Equilibrium I :
Basic Concepts

pH scale

Measurement of pH

Using pH meter

phenolphthalein
or methyl orange
methyl orange
phenolphthalein
no suitable
indicator

strong acid vs
strong alkali
strong acid vs
weak alkali
weak acid vs
strong alkali
weak acid vs
weak alkali

Examples

Add phenolphthalein to the mixture, then

do the first part of the titration (V1).
Thereafter, add methyl orange and do the
second part of the titration (V2).
A mixture of Na2CO3 (V1+V2)
and NaHCO3 (V2)
A mixture of NaOH (V1) and
Na2CO3 (V1+V2)
A mixture of NaOH (V1)
and NaHCO3 (V2)

18. Acid-base Equilibrium II.mmap - 21/5/2005 -

Choosing of
indicator and
pH titration
Curves

Double
indicator
titration

Definition : A solution that resists change in pH when

a small amount of acid or base is added to it.

Composition : A mixture of weak acid and weak base

i.e. usually a weak acid (base) and its salt i.e. the
conjugate base (acid).

In the calculation of the pH of a buffer solution, it is

assumed that the inter-conversion between the acid
(base) and its salt upon mixing is negligible.

The buffering capacity of a buffer solution is depending

on the concentrations of the acid/base and its salt.

Human eyes are only capable to detect a colour change

when the concentration of one coloured substance is more
than 10 times of another coloured substance.

Acid-base indicator is usually a weak acid (base) which

colour is different from its conjugate base (acid).

Buffer solution

Acid-base
Equilibrium II :
Buffers and
Indicators

Acid-base
indicators

reducing agent is
the reagent which
is oxidized in a
redox reaction
oxidizing agent is
the reagent
which is reduced
in a redox
reaction

Remember the
common strong
reducing agents

Remember the
common strong
oxidizing agents

Oxidation
half
equation

Reduction
half
equation

The change in oxidation no. per atom is the same

as the no. of electron being lost or gained by that
particular atom
Figure out the no. of atom that will be oxidized and
the no. of atom that will be reduced by using the
change in O.N.
Add H2O to either side of the equation to get the
number of O atom balanced if necessary.
Add H+ to either side of the equation to get the
number of H atom balanced if necessary.
Check the presence of H+ or OH- on the both sides
to ensure it agrees with the acidity/alkalinity of
the medium used.
For reactions in acidic medium, there should
be no OH- ion on the both sides of the
equation
For reactions in alkaline medium, there
should be no H+ ion on both sides of the
equation

19. Redox Reactions.mmap - 2005/5/23 -

By Combining
two half
equations

By change in
oxidation no.

Check the
medium of
reaction

Balancing
Redox
Equations

Definition
of redox
reaction

Redox Reactions

Oxidation
no.

Oxidation

Reduction

Addition of oxygen atom

Removal of hydrogen atom

Losing of electron

Increase in oxidation no.

Removal of oxygen atom

Addition of hydrogen atom

Gaining of electron

A redox reaction in
which an element
undergoes
oxidation and
reduction at the
same time.

Decrease in oxidation no.

Disproportionation
reaction

the sum of the oxidation no. of

all atoms in a species equals
the overall charge carried by
the species.

no. of proton - no. of electron associated

with an atom assuming that all bonding
electrons are belonging to the more
electronegative atom

Rules of
assigning
oxidation
number

The species on the left of the

table are oxidizing agents.
The species on the right of the
table are reducing agents.

Electrochemical series is constructed by arranging the standard electrode

potentials measured in an ascending order. i.e. the most negative value first.
By convention, the reduction half equations are tabulated
in the ECS. Therefore, standard electrode potential is also
known as standard reduction potential.

Use of
electrochemical
series

Concentration and
temperature
dependence of
electrode potential

Those oxidizing agents at the bottom of the list are strong oxidizing agents
while those reducing agents at the top of the list are strong reducing agents.

Dependence on concentration

The values list in an ECS are all measured at standard conditions

and all species involved are in their standard states.
An increase in concentration of an oxidzing agent will shift the
equilibrium position to the right and make the value more positive.

The value is only depending on

concentration (including partial pressure in
case of gas) and temperature, the size of
the electrode has no effect on the value.

An increase in concentration of a reducing agent will shift the

equilibrium position to the left and make the value more negative.
Nernst Equation
(Not required in HKAL syllabus)
Q : reaction quotient

To predict the overall e.m.f.

of an electrochemical cell

To predict the energetic

feasibility of a redox
reaction

Compare the strengths of oxidizing agents (or reducing agents)

A redox reaction with a
positive overall e.m.f.
will be energetically
feasible.

e.g. disproportionation of Cu+(aq) in water

The feasibility of a reaction is also depending on the

kinetic stability (activation energy) of the system which is
not related to the overall e.m.f. determined.
To ensure the overall e.m.f. of the cell be positive,
E(cell) = E(cathode) - E(anode)
= E(more positive) - E(less positive)

Primary cell

IUPAC Cell
diagram

Electrode potential
(of a half-cell)

Half
cell

Electrochemical cells

Electrochemical Cells

Electrochemical Series
(ECS)

A set of symbols are used to represent the set up of an electrochemical cell.

Symbols
used
Depending on the emphasis and interpretation of the actual setup, it may be
possible to construct more than one IUPAC cell diagram for a given chemical cell.

e.g. Zinc-carbon cell

e.g. Lead acid accumulator

Secondary cell
(rechargeable
cell)

e.g. Hydrogen-oxygen fuel cell

Fuel cell

Some
examples

For a given half-cell, no matter it is being used as a left-hand or right-hand electrode, the reduced form should be placed on the left
if the reduced form and oxidized form are in the same phase. e.g. Pt(s) | Fe2+(aq) , Fe3+(aq) and Fe2+(aq) , Fe3+(aq) | Pt(s)

20. Electrochemical Cells.mmap - 9/5/2005 -

Definition : The difference between the charge on an electrode and the

charge in the solution in which the electrode is immersed in.

Practically, it is not possible to determine the absolute potential of a half cell. Therefore, for the
sake of comparison, the electrode potential of standard hydrogen electrode is defined as 0 V.

The value is depending on the activity of the electrons in the electrode

This value is also related to the nature, including concentration, of the

electrolyte in which the electrode is immersed in.

By definition, overall e.m.f of a cell = E(right) - E(left).

When hydrogen electrode is used as the left-hand electrode,
E(right, the unknown electrode) = overall e.m.f. of the cell

The sign of the electrode potential of the unknown half cell

is the same as the polarity of the right hand electrode
(unknown half cell) in the cell diagram.

In some cases, the solution will be saturated

with the salt and with some insoluble salt
present.
e.g. Ag(s)|AgCl(s)|Cl-(aq)

e.g. Pt(s) | Fe2+(aq) , Fe3+(aq)

e.g. C(graphite) | 2I-(aq) , I2(aq)

Platinized = covered with platinum black

= covered with platinum powder

An inert electrode, e.g. Pt, is immersed

in a mixture of the reduced and oxidized
forms of the reagent concerned.
e.g. Fe3+(aq) /Fe2+(aq) , I2(aq)/I-(aq)

The metal concerned will be used

as the electrode immersed in a
solution containing the salt of the
metal.
e.g. Cu(s) | CuSO4(aq)

By definition, the electrode

potential of an unknown half-cell
is the e.m.f. of an
electrochemical cell measured at
standard condition where a
standard hydrogen electrode
(SHE) is used as the left-hand
electrode and the unknown
electrode is used as the
right-hand electrode.

Involving
metal

Not involving
metal

Standard hydrogen electrode

Pt(s) | H2(g) | 2H+(aq)

Use a potentiometer

Use a voltmeter with high impedance

To measure the e.m.f. of a cell, the current

flowing through the external circuit should be
kept as minimal as possible.

The use of porous partition will create a

junction potential across the partition and
the voltage measured will be different from
the case if a salt bridge is used.

The salt bridge is used to provide cations and

anions to balance the negative and positive
charge cumulated in the two half cells during
the discharge of the cell.

Only KNO3 and NH4Cl are used in the salt

bridge since the migration speed of the
cation and anion are similar and the voltage
reading will not be affected.

The electrodes of the two half cells are connected

together by an external wire.

The electrolytes of the two

half cell are connected
together by using a salt bridge.

In some electrochemical cell,

a porous partition is used to
separate the two electrolytes
instead of using a salt bridge.

Measurement of e.m.f of an
electrochemical cells.

Phase

Definition : region with identical properties.

Phase is not the same as physical state. Usually, there are only 3 physical states i.e. solid, liquid and gas. e.g. Diamond and graphite are both in solid
state but they are two different phases of carbon.
Consider an ideal gas obeying ideal gas law PV=nRT, for a given amount of gas, P is a function of V and T. i.e. P(V,T).

By plotting a graph using

P as the z-axis, V as the
x-axis and T as the
y-axis, a PVT surface of
an ideal gas can be
constructed.

PVT surface of of a
real substance
e.g. water

The isotherms of an ideal gas

shows that no matter how low
the temperature is, the ideal
gas is still a gas and the volume
is always inversely proportional
to pressure.

Isotherms

The projection along

the temperature axis
(Isotherms)

Ideal gas

Isotherms

Real substance
e.g. water

Real gas doesn't obey Boyle's law at low temperature.

Real gas starts condensing at a temp. lower than the critical temp. of the substance.

Phase Equilibrium I :
One-component system
Isochors

PVT surface

As it is
difficult
to study a
3-dimensional
surface,
the
projections
along the
volume
axis and
the
temperature
axis are
usually
studied
separately.

Ideal gas

The isochors of an ideal gas shows that no matter how low the temperature, the ideal gas is still a gas and has zero volume at 0 K.

The diagram is known as phase diagram.

critical temp : above this temperature, gas cannot be compressed into liquid without cooling.
AB : sublimation curve - conditions that solid and vapour can coexist at equilibrium.
BC : vaporization / boiling curve - conditions that water and vapour can coexist at equilibrium.
BD : fusion / melting curve - conditions that solid and liquid can coexist at equilibrium.
B : triple point - the conditions that solid, liquid and vapor can coexist at equilibrium.
BE : supercooling curve - the condition that a liquid exists at a temp. lower than its melting
point and the liquid is at a metastable state. This is because freezing also requires activation
energy. If a liquid is cooled very calmly, the liquid may become supercooled without
solidification.
Real gas condenses at low temperature and becomes liquid and solid.

Phase diagram of
water

Real substance
e.g. water

The
projection
along the
volume axis
(isochors)

Special
features of
the phase
diagram of
water

Special
features of
the phase
diagram of
carbon
dioxide

Special
features of
the phase
diagram of
carbon

21.Phase Equilibrium I . One-component system.mmap - 2005/5/9 -

The fusion curve of water has a negative slope. This implies that the
melting point of water decreases with increasing pressure. When a great
pressure is applied to ice, the open structure of ice will collapse and the
ice will be turned to water.
According to the Le Chatelier's principle, when a pressure is applied to an equilibrium
system, the system will react in a way to minimize the effect of the change imposed. For
ice, it will turn to water which has a smaller volume to lower the increase in pressure.

Like most substances, the fusion curve of carbon dioxide has a positive
slope. This implies that the melting point of carbon dioxide increases
with increasing pressure.
The triple point pressure is higher than atmospheric pressure. This implies that dry ice will
sublime directly to gaseous carbon dioxide without going through the liquid state.

It is possible to convert graphite to diamond by applying pressure to

graphite. However, the rate of conversion is very slow as this involves
rearrangement of atoms in solid state.
If graphite is heated to molten state and allowed to crystallize under high pressure,
artificial diamond can be made. Moreover, the crystallization is very fast comparing with
the natural process of formation of diamond, the diamond crystal obtained will be small
and may not be suitable for making jewelry.

The components cannot be

separated by fractional
distillation completely.

Positive
deviation

Extreme negative
deviation
(a solution of
involatile solute)

Negative
deviation

Extreme positive
deviation
(2 immiscible liquids)

Azeotropic mixture (or constant boiling mixture) - A mixture with a constant composition
when it is being boiled continuously.
i.e. the composition of the liquid mixture = the composition of the vapour
The 2 components vaporize independently and give a total
vapour pressure higher than that of either component.

The lowering of vapour pressure will cause depression in melting point and elevation of boiling point of the solvent.

22. Phase Equilibrium II . Two-Component System.mmap - 19/5/2005 -

Deviation from
Raoult's Law
(non-ideal solutions)

Difference between
1-component and
2-component systems

Phase Equilibrium II :
Two-Component System

Raoult's Law

For a 1-component system, the (saturated) vapour pressure

(P) of a substance is a constant at a given temperature.

In a 1-component system, the properties of a substance is a function of P and T. This requires a 3-dimensional space to represent.
Instead of studying the problem in a 4-dimensional space, the study will be limited to the case in which a liquid and its
saturated vapour coexist in equilibrium.

In a 2-component system, the

properties of a substance will
be depending on P, T and X
(mole fraction) which will
need a 4-dimensional space to
represent.

For a 2-component system, the (saturated) vapour

pressure at a given temperature will be a function of X
(mole fraction) of the component present.

The boiling point of an ideal solution varies linearly with the composition approximately.

Partition of a solute
between 2 phases

Phase Equilibrium III :

Three-Component
Systems

23. Phase Equilibrium III . Three-Component Systems.mmap - 2005/5/23 -

Solvent Extraction
(between 2 immiscible
solvents)

Partition of a solute between 2 immiscible solvents

Partition Law - At a
given temp. and at a
state of equilibrium,
the ratio of
concentrations of a
solute in two
immiscible solvents is
constant.

At equilibrium, the rates of diffusion of the solute between two

immiscible solvents in opposite directions are the same.

As the unit of concentration

will be canceled out in the
calculation, the unit can be
expressed in any unit and
partition coefficient will have
no unit eventually.

Most common organic solvent are lighter than water except chloroform(CHCl3), tetrachloromethane(CCl4) and
1,1,1-trichloroethane

e.g. The partition law is not applicable to the case where ethanoic
acid is partitioned between hexane and water as ethanoic acid exists
as dimmer in hexane (non-polar solvent) and as monomer in water
(polar solvent)

If the density of the solvents are not known, when we say solute A
is partitioned between solvent B and C, it usually means

The law is only application to the case if

the solute has the same molecular
structure in the two solvents.

Partition of a solution between a

stationery phase and a mobile phase

Mobile phase

Stationery phase

e.g. different kind of solvent or mixture of solvents

e.g. silica gel on an aluminium foil

e.g. the microscopic water film on the surface of the chromatography paper

It would be more effective to carry out a solvent extraction in successive extractions, a small portion at a time, for a given amount of solvent.

Paper Chromatography
(between a stationery phase
and a mobile phase)

At a given temperature, with a

given chromatography paper
and a given solvent, the solute
being analyzed is
characterized by its Rf value

Analysis of amino acids - A mixture of colourless amino acids can be separated by paper
chromatography. The positions of amino acids spot in the chromatograph can be detected by spraying
with ninhydrin (a developer), which reacts with amino acids to yield highly coloured products (usually
purple in colour).