Idea of atom introduced

Democritus
No experimental evidence Becquerel Discovery of radioactivity
Atom is the smallest unit of
matter and is not breakable Extraction of radium and
Curie polonium
With experimental evidence Dalton History of discovery
from the study of gas
Study the nature of , and
Invention of cathode ray tube Goldstein Rutherford radiation
Negatively charged Behaviour of cathode ray in Development of atomic fast moving helium nuclei
magnetic and electric field particle
fast moving particle
model 5% of speed of light
Invention of the word "electron". Thomson very fast moving electron
Nature of radioactivity particle
Atom is no longer unbreakable Raisin pudding model of atom up to 99% speed of light
high energy EM wave
Gold foil scattering experiment radiation
Rutherford 100% speed of light
The idea of presence of tiny nucleus
replusion among proton
Discovery of neutron Chadwick binding force between proton
particle
and neutron
The idea of nucleus is breakable Study of radioactivity
lowering of p:n ratio
instablility of neutron when
Vaporization chamber isolated
Radioactivity Origin of radioactivity particle
Ionization chamber increasing of p:n ration
Accelerating plates Nature state of atoms after
Deflecting magnetic field Construction the big bang / nucelus
formation
Detector
Recorder Atomic Structure radiation re-orientation of the spinning
proton
Vacuum Pump
Mass spectrometer Meaning of Half-life
To determine the ionization Working principle - response to Natural decay First order reaction
energy of an atom m/e ratio Nuclear Reaction Constant Half-life
Independent of temp.
Determination of isotopic mass Artificial transmutation
Determination of atomic mass Interpretation of mass Mass of an atom
spectrum Leak Detection Geiger-Muller counter
Determination of molecular mass
Determination of molecular structure I-131 (thyroid disease)
Bio-tracer
The relative mass of a particular isotope in C-12 scale where P-32 (metabolism of plant)
C-12 isotope is defined to have exactly 12 units of mass. Relative isotopic mass Use of Radioactive isotope I-131 (thyroid cancer)
Radiotherapy
Co-60 / Cs-137 (tumor)
The weighted average of the relative isotopic masses for a particular
element in C-12 scale according to their natural abundance Relative atomic mass Carbon-14 dating
Nuclear power Nuclear bomb
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. Relative molecular mass
1. Atomic Structure.mmap - 2005/5/23 -
 Boyle's Law P 1/V
Charles' Law V T
Avogadro's Law V N
Volatile liquid vaporizes easily by heating
No interaction among particles
Individual particle occupies no volume
Assuming the vapor behaves ideally
Molecular mass is numerically the
same as molar mass Principle
Definition
particles are Avogadro constant
interaction among particles is negligible moving fast How many ?
High temperature (Experimental
Conditions a real gas behaves How measurement required)
virtually ideal much
particles are Molar
space occupied by individual particle is negligible far apart is one Carbon-12 Scale
Low pressure mass
mole ? How heavy ?
Barometer in the laboratory Measurement of P Molar volume
Molar
Some liquid may have r.t.p.
How large ? volume
not vaporized Take reading only when the Increase in volume of of a gas s.t.p.
The vapor may be still reading is steady Precaution the gas syringe
Measurement of V Avogadro's law
expanding
The liquid may leak out.
Volatile liquid usually Hold the hypodermic
has low surface tension. syringe horizontal
Difference in mass of
Body warmth may heat up the hypodermic syringe Determination
the liquid and expel it from before and after of molecular mass Ideal gas Law
Hold the end of the
the syringe syringe only injection of a volatile liquid / Equation Behaviour
Precaution
PV = nRT of Ideal gas
Inject the liquid into the Measurement of m
deeper part, usually hotter,
of the gas syringe to Insert the needle fully
ensure better vaporization. Setup of
into the gas syringe
apparatus Mole Concept
The system may have not Take reading only when the Thermometer
reach thermo-equilibrium yet. reading is steady
Precaution (final reading)
Measurement of T
Relationship between
Current I, Amount of charge
Q and time t i.e Q=It
Faraday's
Laws
1st Law m Q
of
Charges electrolysis
2nd Law m 1/n
Charges carried by Faraday constant
1 mole of electron
Allow the system to reach a thermo-equilibrium 1 F = 96500 C
Take all initial readings Operation
Take final reading when all readings are steady
Definition of partial pressure - the pressure
of a component in the gaseous mixture if Total pressure of a gaseous
that component occupies the same volume mixture is the same of the sum
by itself alone. of the partial pressure of all of Dalton's Law of partial
mole fraction (percentage by number) the component present pressure
2. Mole Concept.mmap - 21/5/2005 -
 A solution with accurately known concentration Standard solution
Process of determination of concentration of a
non-standard solution Standardization
A substance which can be used to prepare a
standard solution directly
known composition
stable composition Titration
Primary standard
readily soluble criteria
preferably with higher
molecular mass
Empirical formula Simplest whole number ratio
The point at which the 2 reagents just react with
each other completely. Equivalence point Formulae of
Molecular formula Actual no. of atoms
Compounds
The point when the end of titration is detected End point
Structural formula Connectivity of atoms
methyl orange or
Formulae By Combustion Analysis
phenolphthalein strong acid vs strong base Empirical formula
Choice of From Composition by mass
Determination
methyl orange strong acid vs weak base indicator of Formulae From empirical formula and
Using indicator
molecular mass
phenolphthalein
Volumetric Molecular formula
weak acid vs strong base Water of crystallization
Analysis
Acid-base
pH meter (titration curve) titration
thermometric titration
Chemical Equations
Without indicator
and Stoichiometry
methods for titration of
weak acid vs weak alkali conductometric titration
iodine / potassium iodide
Word Equation
starch solution
Stoichiometry
sodium thiosulphate Iodometric titration Chemical Equation
Chemical Equations Stoichiometric coefficients
Determination of concentration of Redox titration
chlorine bleach Reacting masses
Calculation based on equations
KMnO4 vs FeSO4 Volumes of gases
Constant heating is required KMnO4 vs H2C2O4.2H2O
Determination of percentage by mass of calcium
carbonate in chalk
Example
Analysis of aspirin Back titration
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 -
 gas discharge tube
slit
Setup of the apparatus
prism or diffraction grating
photographic film
Numerous lines
Different series
Characteristic of the hydrogen Unevenly spaced lines in each
spectrum series
Convergence limits at the
higher frequency end of each
series Continuum
Introduction of concept of
quantum Planck's equation
Line spectrum Process of excitation and ground state
Atomic Emission spectrum of relaxation
hydrogen excited state
Interpretation of the hydrogen Presence of numerous energy principal
spectrum levels (shells) quantum number
Numerous lines
Multiple transitions take place at the same time
Unevenly spaced lines Unevenly spaced energy levels
Bohr's model
Convergence limit
and continuum Ionization of atom
Flame test Atomic emission spectroscopy
Discovery of helium
Uniqueness of atomic emission As a mean of identification Identification of element at
spectra remote star
Red shift
Different models of Neon light with different
atom colours
Definition
Successive ionization energies Evidence of shell
Ionization energies
The Electronic 1st ionization energies across
periods Evidence of subshell
Structure of Atoms
Electrons are orbiting around the nucleus in orbits with with different energy
The allowed energy of the electron in an atom is quantumized
Features of Bohr's model
Able to explain the emission spectrum of hydrogen spectrum but fail to explain the emission spectrum of those
multi-electron system.
Wave-particle duality of electron
Electromagnetic Spectrum
Heisenberg's uncertainty principle
Continuous Spectrum Background knowledge
By mathematical modeling
Line Spectrum
n = 1,2,3 ...
principal energy
Principal (n)
size
shell no.
l = 0,1,2...(n-1)
shape of orbital / subshell
Wave-mechanical model / Quantum numbers Subsidiary (l)
Orbital model energy in multi-electron
system
m = -l,...,0,...+l
Magnetic (m)
spatial orientation of orbital
s = +½ or -½
Spin (s)
spin of electron
Pauli Exclusion principle
Radial probability distribution
Orbital / Electron cloud representation Nodal surface
Nodal plane
4. The Electronic Structure of Atoms.mmap - 19/1/2005 -
 Electrons occupy the orbital with the lowest energy first
Aufbau Principle
Gets more endothermic when Value reflects the net Order of energy of different orbitals
increase in attraction with e- Energy required to
attraction between remove 1 mole of
> increase in repulsion among All electrons behave different in an atom i.e. no 2
the outermost electron electrons from 1
electrons, and vice versa electrons in an atom have the same set of quantum no.
and the nucleus mole of gaseous Pauli exclusion principle Each orbital can accommodate
Energy required to move the outermost electron to infinity atom
Definition 2 electrons with opposite spin
and escape from the attraction of the nucleus
Electrons will occupy degenerate orbitals singly
Nuclear charge Hund's Rule (Rule of Maximum Multiplicity) with parallel spin before pairing up occurs.
Attraction with the nucleus
Effective nuclear
Relative charge (nuclear Building up of electronic Energy of 4s orbital is only a little
repulsion with Primary charge - shielding
position of the configuration on paper bit lower than that of 3d orbital
the inner e- shielding effect)
effect outermost e- The difference gets even smaller when 3d electrons shield 4s electron from the nucleus
usually stronger (Electronic experienced by and make 4s electrons more energetic
the outermost e- 3d orbitals are being filled up
configuration of
repulsion with the Secondary Repulsion
the atom) Depending half-filled 3d and 4s orbital
e- in the same shell shielding among
effect electrons on less repulsion
Irregularity no electron pair-up in 3d and 4s
usually weaker Chromium
Position of the outermost e- (Size of atom) more evenly distributed electron cloud less repulsion
Exception
the increase in nuclear charge full-filled 3d and half-filled 4s orbital
outweighs the increase in Copper less repulsion
Getting more endothermic more evenly distributed electron cloud
secondary shielding effect across a period
the increase in primary Main trend Variation by notation
shielding effect outweighs the Getting less endothermic down Representation of
increase in nuclear charge by electron in boxes
a group electronic configuration
Noble gas cores e.g. [He], [Ne] etc.
Variation of First use of abbreviation
Imply presence of subshell Completely filled quantum shell e.g. K, L, M
Ionization energy
Imply pairing up of electrons in an orbital General
pattern
across the first 20
Electron goes into a more elements the p to e- ratio is increasing
energetic p-subshell Successive ionization energy is always
Showing 2-3-3 much higher than its predecessor the repulsion/shielding among electron is getting less
(or full filled s-subsell in Be Unexpected drops pattern across more difficult to remove electron from a positive particle
and Mg - more evenly
distributed charges)
at B and Al period 2 and 3 Electronic
(or peaks at Be and Mg) the increases in successive ionization energies are too
configurations and
Plot of Successive ionization In log scale large to be represented by linear scale
Electrons starts pairing up in O the Periodic table Variation of Successive energies of an atom
and S - extra repulsion (or half Unexpected drops ionization energies appear in tiers Proof of the presence of shells
filled p-subshell in N and P - at O and S
more evenly distributed charges) (or peaks at N and P)
shift upwards the p to e- ratio is increasing
Plot of successive ionization
energies of different atoms the electronic configuration of an ion is the same as
shift to the right the electron configuration of the preceding atom
including metallic radius
half of the distance between 2 chemically
bonded nuclei of the same element
Attraction with the nucleus Nuclear charge
Primary repulsion with
shielding the inner e-
Depending Relative position of the effect
on outermost e- usually stronger
Repulsion (Electronic configuration
Covalent radius Secondary
among of the atom) repulsion with the
Atomic radius electrons shielding e- in the same shell
effect
usually weaker
the increase in nuclear charge outweighs the increase in
contract across a period secondary shielding effect.
General trend
the increase in primary shielding effect outweighs the
s-block, p-block, d-block and f-block elements expand down a group increase in nuclear charge
Periodic Table
half of the distance between 2 nuclei of the same element which
van der Waals' radius are not chemically bonded together in a crystal lattice
5. Electronic configurations and the Periodic table.mmap - 6/1/2005 -
 The link between the microscopic interaction among
298K
Standard conditions Significance particles and macroscopic observable change.
1 atm
pure, if it is a liquid or solid
Enthalpy change Definition : heat change of a system at constant pressure
most stable form at 298K, 1 atm Standard state Enthalpy
1M if it is an solution and Definition : heat change of a system at constant
Different forms of the same element / Internal Internal energy change volume
compound in the same physical state Presence of allotrope and energy
e.g. graphite and diamond, polymorph Relationship between Enthalpy Enthalpy change = Internal energy change +
Need of standard state and
ozone and diatomic oxygen change and Internal energy Work done on the atmosphere
condition
change
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
Heat of Neutralization Heat flows out of the system because of the
Neutralization of strong/weak acid / alkali increase in temperature of the system
A solution with specific concentration / Exothermic Potential energy among the particles is converted
an infinitely dilute solution is prepared. Heat of Solution process to heat energy when there is an overall
strengthening of attractions among the particles.
1 mole of compound is formed from its constituent Exothermic and Bond formation > Bond breaking
elements in their standard states Heat of Formation Examples and definitions Endothermic process Heat flows into the system as the temperature
of the system decreases
Complete combustion of 1 mole of a specific
substance in excess oxygen Heat of Combustion Endothermic Heat energy is converted to potential energy
process when there is an overall weakening of attractions
Formation of 1 mole of hydrated crystal among the particles.
from anhydrous solid Heat of Hydration Bond formation < Bond breaking
Standard enthalpy
Experimental setup bomb calorimetry to changes
The total enthalpy change of a chemical reaction is independent
conversion to enthalpy change determine the internal
of the route by which the reaction takes place
by calculation energy change
Another version of law of Energy cannot be created or
Energetics destroyed
conservation of energy
Philips Harris calorimeter to Energy cycle & energy level diagram
Experimental setup determine heat of combustion
Born-Haber cycle as energy cycle used
Hess's Law to determine the heat of formation
Polystyrene cup + cover
Some changes has no direct reaction at all
Insulating layer
Experimental setup The direct reaction may be too vigorous
thermometer
and too dangerous to be carried out
stirrer Need of Hess's Law
The extent (% of conversion) of
Specific heat capacity of reaction cannot be controlled.
solution is the same as that of Formation of side products
water Experimental determination
The rate of heat loss is simple calorimetry to
uniform / No heat loss to the determine the enthaply Balanced equation according to definitions
surrounding. change Calculation involving heat capacity
Prerequisite
The heat capacity of some Calculation of mole
components in the system can Common
Patience and careful manipulation
be ignored. assumptions
The specific heat capacities of Some common references in 1. Constituent elements
Calculation
some components are only constructing energy cycles 2. Combustion products
approximation. 3. Constituent atoms
Heat evolved will be the same
as heat flow in the original + and - sign must be included
definition of enthalpy change unit and sign of the answer Unit, usually in kJmol-1 must
be included
6. Energetics.mmap - 17/1/2005 -
 Heat of formation formation of 1 mole of compound
formation of 1 mole of gaseous
atoms
Atomization energy of element
always positive
Balance between Removal of 1 mole of electrons
Attraction among oppositely from 1 mole of gaseous atoms
non-directional
charged ions / ions
electrostatic attraction Ionization enthalpy of atom
Repulsion among similarly always positive
and repulsion
charged ions
Addition of 1 mole of electrons
Potential well diagram to 1 mole of gaseous atoms /
ions
negative : attraction between the incoming
electron and the nucleus > the repulsion between
Born Haber Cycle
face centered cubic the incoming electron and the existing electrons
C.N. = 6 for both ions e.g. NaCl Electron Affinity of atom
(f.c.c.) structure positive : attraction between the incoming
electron and the nucleus < the repulsion
C.N. = 8 for both ions Different
e.g. CsCl between the incoming electron and the existing
simple cubic structure arrangements
electrons
of lattice points
Stoichiometry of the Formation of 1 mole of ionic
compound Actual arrangement is
compound from its constituent
depending on
ionic radius ratio gaseous ions
Energetics always negative
Determination of empirical Coordination number (C.N.) - of
formula no. of nearest neighbour depending on charge density
formation Lattice energy of ions involved
a measure of strength of ionic
1. the smallest unit containing depending on the packing
bond
all the fundamentals of a crystal efficiency i.e. crystal
without repetition. Ionic Bonding arrangement
2. the smallest unit of a crystal Positive metal ion + free electron are actually more
from which the original crystal Definition Limitation of using stable
Unit Cell energetic (less stable) than a gaseous metal atom
structure can be recreated by electronic configuration to
repetition in 3-dimensional space. explain Indeed, the stability of an ionic compound is mainly
arising from the formation of ionic bond among
Determination of Determination of no. of oppositely charged ions.
empirical formula different ions in an unit cell
Ionic Construction of Born Harber cycle for
crystals the naturally occurring ionic
The position of a formula unit
compound e.g MgCl2
of the compound considered. Lattice point
Stoichiometry Nature prefers the Hypothetical lattice energy
of stoichiometry with calculated from the ionic model
Definition - Distance from the centre of an ion to
ionic the most exothermic Construction of Born
the point of zero electron density between 2 Some terms The lattice
compounds heat of formation Haber Cycle for the
adjacent ions. arrangement of the
i.e. highest stability hypothetical ionic
determined by X-ray comparing with the compounds hypothetical compound
Assumptions
Electron density map diffraction constituent elements e.g. MgCl and MgCl3 is known
of
ionic All ions are perfect spheres
polyatomic ion model Cations and anions are just in
is bigger than no. of atoms contact with each other
simple ion present
Value The bond is purely ionic
In general, negative depending on ionic radius The value of heat of formation is mainly determined
ion is bigger than by the values of ionization energies and lattice energy
positive ion p to e- ratio
As the no. of electrons and
electronic configurations are the Size of
same, the size is only depending isoelectronic
on the number of protons present. ion
7. Ionic bonding.mmap - 19/1/2005 -
 In the range of 150-1000 kJmol-1
Bond Dissociation Energy
Energy required to break a particular bond D(X-Y)
The average energy required to break a type of bond (Average) Bond
Estimation using enthalpy change of atomization enthalpy/energy E(X-Y) Attraction between nucleus,
bonding electron and another
Using bond energy to estimate the enthalpy change of a reaction Balance between nucleus directional attraction
no. of bonding electrons / 2 Bond order electrostatic attraction
Replusion among the electrons
and repulsion
The longer the bond length, the weaker will be the Replusion between the nuclei
Strength of Covalent
bond Potential well diagram
bond
(Primary) shielding effect affects the nuclear
attraction experienced by the bonding electrons
Constructive interference of
Estimation of bond length Bond length
Factors affecting bond atomic orbitals
Atomic size
Polarity of bond Breakup of additivity of (covalent radius) strength Overlapping of atomic orbital Increase in electron density
covalent radius along the inter-nuclear axis
Resonance
Promotion of paired electrons
covalent bond with certain ionic character is found to be
to low lying energy orbital
stronger than purely covalent or purely ionic bond bond polarity (e.g. 2p comparing with 2s, 3d Formation of
comparing with 3p) to yield more bonds
e.g. weak F-F, O-O and N-N repulsion among the lone pairs Formation of more unpaired electrons for
bond Pairing up of More overall
on adjacent atoms covalent bond unpaired electrons bond formation
exothermic change
(bonding electrons)
High overall stability
Electron centres : lone pair,
single bond, double bond, a covalent bond in which the
triple bond bonding electrons are supplied
by one atom only
Electrons centres tend to
separate from each other as Overlapping of a lone pair with
Dative covalent bond
far as possible to minimize a vacant orbital
mutual repulsion Valence shell electron pair Covalent bonding e.g. NH4+, H3O+ NH3BF3, Al2Cl6
repulsion between lone repulsion theory
pair-lone pair > lone pair-bond Shape of molecules and # of p - # of e- associated with
pair > bond pair-bond pair polyatomic ions
Electrostatic repulsion is very an atom assuming that bonding
lone pair always occupies sensitive to distance e- are equally shared
Formal charge
equatorial position in a five
electron centres system # of p - # of e- associated with
linear, angular (V-shaped or bent), trigonal planar, tetrahedral, trigonal an atom assuming that all
pyramidal, trigonal bipyramidal, seesaw, T-shaped, octehedral, square bonding e- are belonging to
planar Oxidation number the more electronegative atom
In the describing of the shape of molecule, the presence of lone pair is Description of shapes
3s orbital has much higher
not included. Drawing of Lewis Period 2 elements never energy than 2p orbital
structure excess octet
Energetically unfavorable
tetrahedrally arranged Cases obeying
octet rule an electron acceptor with a
strong C-C single bond only Diamond Can be less vacant p-orbital for dative
high hardness, high melting point, electrical insulator, excellent heat conductor than octet bond formation
e.g. BF3
arrange in hexagonal layers
strong C-C bond, bond order 1 1/3, within layer Availability of low lying energy
Giant Covalent Structure
Graphite Cases not obeying orbital (e.g. 3d orbital
weak van der Waals force between layers
octet rule comparing with 3p orbital)
low hardness, very high melting point, conducting along the layer, slippery Expansion of octet
e.g. PCl5, SO42-
between layers
high hardness, high melting point Quartz (SiO2)
8. Covalent bonding.mmap - 2005/5/21 -
 Assumptions
The lattice arrangement of the compound is known, if it is hypothetical
of simple
ionic All ions are perfect spheres
model Cations and anions are just in contact with each other
and clearly separated from each other
The bond is purely ionic. i.e. no sharing of electron or incomplete transfer of electron
A more agreed value implies
a situation similar to the
assumptions of ionic model -
pure ionic bond e.g. NaCl (almost purely ionic)
The lattice energy
calculated based on Mutual repulsion
the ionic model is The ions are not of electron cloud
The bond is never the same as A very different perfectly in an ionic lattice
e.g. Cl2 non-polar The bonding electrons the experimental value implies failure
are shared equally spherical Polarization of
Pure covalent bond value of the ionic model -
anion
with strong
atoms have different covalent character Ions may not Certain covalent
e.g. HCl electronegativity The bonding electrons
clearly separated character
are not shared equally Starting from
from each other Polarization of
pure ionic bond
Definition - product of quantity of charge (q) anion
and distance of charge separation (d)
Polarization - distortion of electron cloud
The dipole moment along a bond is pointing from (Permanent) of anion under the influence of cation e.g. AgCl, AgBr, AgI, ZnS
Dipole For all real
the less electronegativity atom to the more
moment ionic compounds
electronegativity atom ease of distortion of
Contribute a dipole moment electron cloud
pointing away from the atom Lone pair p to e- ratio
inversely proportional
Anion is always to the nuclear primary
polarized by Polarizability
Depending on the vector attraction on the shielding
Geometry of the molecule the cation of an anion
sum of all dipole electron cloud effect
magnitude of individual moments Starting from electronic
pure covalent configuration secondary
dipole moment
shielding
bond
A molecule with non-polar Polar effect
bond only covalent
directly proportional to the
bond
A molecule with all dipole Polarizing power of a cation charge density of a cation
moments canceling out each
other
Non-polar molecules Non-polar Intermediate Type of
are also attracted by molecule Polarity Bonding Increase across a period and
an electric field as a Do not / of a
up a group
weak temporary dipole weakly molecule Tendency of an atom to
moment will be attract the bonding electron in Not applicable to noble gases
attracted by
induced onto them by an electric a stable molecule Depending on the effective
the electric field field nuclear charge experienced by nuclear charge
the bonding electron
shielding effect
A molecule with non-zero
net dipole moment reflects the attraction on the
May not be able to tell the ionization energy outermost electron in an atom
actual direction of the net Polar molecule (Dipole) Electronegativity
dipole moment reflects the attraction on the
Pauling's scale
Attracted by an electric field incoming electron to be added
electron affinity to an atom
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
9. Intermeidate type of bonding.mmap - 26/1/2005 -
 lattice of positive ions
Sea of electrons model immersed in a sea of
delocalized electrons
Electrostatic attraction among positive
ions and sea of delocalized electrons Non-directional in nature
metallic radius = covalent radius
Nature of metallic bond agitation of delocalized
high conductivity electrons
unique
properties of high ductility and delocalized electrons capable to reform the
metal malleability metallic bond even if the positive ions are shifted
delocalized electrons get
metallic luster excited and give out luster
In the range of 100-500 kJmol-1
Attraction on the delocalized Charge density of the positive
electrons ion e.g. Na+ > K+ > Rb+
Metallic bonding Strength of metallic no. of valence electrons e.g.
bond Availability of delocalized Al > Mg > Na
electron high charge density of the positive ion limited the
availability of the valence electrons e.g. Hg
Big difference between m.p. In molten state, most metallic
and b.p. bond are not broken
hexagonal close packing C.N. = 12
(h.c.p.)
abab... pattern
(face centred) cubic close C.N. = 12
close-packed structure (74%) packing (f.c.c. or c.c.p.)
Metallic crystal (Giant abcabc... pattern
metallic structure) tetrahedral holes and
octahedral holes
body centered cubic (b.c.c.) C.N. = 8
open-structure (68%)
Determination of no. of atoms
in an unit cell
10. Metallic bonding.mmap - 22/2/2005 -
 An exceptionally strong directional dipole-dipole interaction
H on F, O and N hydrogen atom bonded onto a very
electronegative atom / entity Attraction between a
permanent separation of centre of positive charge and centre of negative charge
including H on CHCl3 naked proton and a lone permanent dipole
pair possessed by all polar molecules (dipoles)
lone pair on F, O and N only lone pair on a very electronegative atom
Type of dipole (polar the fluctuation of electron cloud creates
instantaneous/temporary an instantaneous dipole
difference in electronegatvitiy molecule) dipole
possessed by all kinds of molecules including polar molecules
2 per H2O molecule, 1 per HF, average no. of hydrogen bond overall strength depends on
NH3, MeOH molecule per molecule induced by a permanent dipole
Strength (1/10 of covalent bond) induced dipole
5-50 kJmol-1 induced by instantaneous dipole
Hydrogen bonded molecule has higher boiling point that
ordinary polar molecule with comparable size. hydrogen bonded molecules also
e.g. HF, H2O, NH3, MeOH comparing with other possesses van der Waals' forces Real gas does individual particle occupies no
molecules with comparable size not obey ideal volume
gas law assumption of
Mixing trichoromethane and ethyl ethanoate perfectly ideal gas law no interaction (attraction and
H-bond formation
repulsion) among particles
Experimental
Mixing ethanol and hexane H-bond breaking Estimation of strength of hydrogen bond
Evidence
Period 2 hydrides comparing with hydrides of period 3 to 5 Real gas equation
formed between molecules
a - attraction among particles
(usually) gives higher b.p. van der Waals' constants
b - volume of individual particle
formation of new
Condensation of solid and liquid at low temp.
intermolecular forces >
breaking of old intermolecular also called permanent
a substance would be soluble forces intermolecular intermolecular and dipole-permanent dipole
intramolecular hydrogen interaction
ability to form hydrogen bond with water (usually) gives higher solubility bond dipole-dipole interaction attractions among opposite
overall polarity of the molecule in water ends of permanent dipole
e.g. trans-butenedioic acid (actually more important than
ability to form H-bond) also called permanent dipole
e.g. alcohols induced dipole interaction
formed within a molecule dipole-induced dipole
a permanent dipole induce a
intramolecular interaction the opposite ends attracted
(usually) gives a lower b.p. temporary dipole onto another
prevents the formation of intermolecular hydrogen bond each other
polar/non-polar molecule
forming bond is better than Origin
dimerization of carboxylic dispersion force
not forming bond acids in vapour state /
non-aqueous solvent London force
forming strong bond is better
than forming weak bond other names temporary dipole-temporary
dipole interaction
highest density at 4 °C Hydrogen bond van der Waals forces instantaneous dipole-induced
dipole interaction induced dipole-induced dipole
water expands upon freezing interaction
six membered rings of O linked Low density of ice the opposite end of different
by O-H▪▪O linkage diamond like structure open structure of ice Intermolecular an instantaneous dipole induce
temporary dipoles attract each
a temporary dipole on another
Forces molecule other
with dipole-dipole
interaction, dipole-induced stronger overall
dipole interaction and strength for
instantaneous molecules with
dipole-induced dipole comparable size higher b.p. and m.p.
Polar interaction
molecules
Strength (1/10 of weaker overall strength
with instantaneous for molecules with
covalent bond)
dipole-induced dipole comparable size lower b.p. and m.p.
unique properties of water 5-50 kJmol-1
interaction only
branched isomer
Examples Non-polar increases with increasing of hydrocarbon
molecules depending on the molecular size / surface area has lower boiling
thermal expansion of solid point
density drops polarizability of e.g butane vs 2-methylpropane
structure
from below 0 °C to 0 °C the molecule
polarizability of constituent atoms
melting of ice e.g. telfon/poly(tetrafluoroethene)
density increases sharply at 0 °C Variation of density with half of the internuclear distance between 2 atoms
rapid collapsing of open structure
temperature (K.E.) of the same element which are not chemically
continuous collapsing van der Waals' radius bonded together in a crystal lattice
density increases continuously of open structure
from 0 °C to 4 °C
still possesses certain hexagonal network
density drops thermal expansion of liquid water face-centred cubic structure
from 4 °C to 100 °C
iodine (f.c.c)
hydrogen bond between N-H and C=O group among different amide Molecular crystal
groups along the polypeptide chain single helical structure Protein face-centred cubic structure
dry ice (f.c.c)
formation of secondary
hydrogen bond between
3 H-bonds cytosine - guanine pair structure in protein and DNA
heterocyclic bases on 2
separate strands DNA
2 H-bonds thymine - adenine pair double helical structure
11. Intermolecular Forces.mmap - 2005/5/23 -
 e.g. H2O, NO2, S8, P4
under 100 atoms fat and oil - marginal cases, with just over 100 atoms
Simple molecular usually gases, liquids or low melting solids
weaker intermolecular forces soft and weak
solubility depending on the polarity of the solute and solvent In general, like dissolves like
Molecular structure
e.g. starch, protein, plastic
Macromolecular over thousands of atoms
stronger intermolecular forces usually solid
non-conducting no delocalized electrons
e.g. diamond, quartz, graphite
hard
high density
high melting point
insoluble in any solvent intermolecular forces never stronger than covalent bond
strong covalent bond
usually non-conductor of
electricity bonding electrons in most covalent bonds are not delocalized
Exception - diamond is an the rigid structure transmits the
excellent conductor of heat vibration of the C atoms efficiently
usually poor conductor of heat
Giant covalent structure
weak van der Waals' forces between layers
Structure and brittle
properties of flat hexagonal layers
materials slippery
weak van der Waals' forces between layers
conducting presence of delocalized electrons along the hexagonal layers
Speical case : Graphite
high melting, even higher than diamond strong C-C bond, bond order 1 1/3
Giant structure weak van der Waals' forces
lower density than diamond large space between layers between layers
high m.p. and b.p.
hard
strong ionic bond high density
slight dislocation brings ions of similar charge together repulsion cleaves the crystal
brittle
Giant ionic structure
the ions are not free to move in solid state only conducts in molten or aqueous state
presence of ions
dipole - ion interaction
If soluble, only soluble in aqueous solvent
increase in disorderness
high m.p. and b.p.
sometime, strong metallic bond hard
high density
Giant metallic structure
malleable and ductile
Presence of sea of delocalized electrons
high conductivity of heat and electricity
Soluble in mercury
12. Structures and properties of materials.mmap - 2005/6/5 -
 Other possible units : mol, g
For gases : Pa, mmHg, atm,
Change in quantity per unit time Quantity is usually expressed in moldm-3 cm3, dm3
Time is usually expressed in s
Depending on the units of quantity and time v
Unit of rate of reaction
Usually expressed in moldm-3s-1
Definition of Rate
Average Rate
Instantaneous rate
Different rate
Initial Rate
(Instantaneous rate at t = 0)
Differential form of rate equation / law
by sudden cooling
by dilution with a large amount of water
By titration Quenching of reaction before titration is done
Constant time approach by removing the catalyst
(fix the time interval by removing one of the reactant
and determine the
amount present) Measuring of volume of gas
By measuring a physical quantity related to the Transmittance and Absorbance
Measuring of colour intensity
amount of a chemical Need of a calibration curve
Measuring of mass of the
reaction mixture
Rate of Chemical
Reactions constant amount of S ppt.
Disproportionation of produced to mask the cross
Na2S2O3 in acidic medium
constant amount of methanal reacted / HSO3- consumed
Methanal Clock
Concentration of reactants Measuring of experiment
Pressure Reaction Rate
Factors affecting
Temperature Constant amount approach
Reaction Rates (fix the amount to be
Surface Area phenolphthalein
reacted and determine
Catalyst the time required to indicator
Light complete the reaction)
constant amount of I2 produced / S2O32- consumed
Iodine Clock
experiment
I- vs H2O2
starch indicator
Reaction constant amount of Br2 produced / phenol consumed
between Br- and
BrO3- in acidic
medium
methyl red
indicator
13. Rate of Chemical Reactions.mmap - 2005/6/5 -
 Differential form

Order with respect to individual reactant

Order of reaction
Overall order of the reaction
Unit of rate constant is depending on the overall order of
the reaction
Rate constant k
A value depending on temperature only
the rate is independent of the
concentration of the reactant
Ordinal form
Zeroth order Usually occurring in catalyzed reaction
where the availability of the catalyst
surface is the limiting factor of the rate
Different order with
respect to a reactant the rate is directly proportional to the
First order concentration of the reactant

the rate is directly proportional to the

square of the concentration of the
Second order reactant

Rate Equation / Law Zeroth order reaction

half life

The concentration of C-14 in

atmosphere is assumed to be
constant
Rate Equations and Integrated First order The percentage of C-14 in a living
Order of Reactions form reaction organism is assumed to be constant.
half life By comparing the percentage/beta
carbon-14 emission of C-14 in an archaeological
dating 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 zeroth order
Straight inclined line
time

Horizontal line zeroth order

Determination of
rate equation / law By plotting rate against
first order
By plotting By trial and concentration Straight inclined line
graph error
parabola 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 The slope will be the order of reaction with
(concentration) respect to the reactant

14. Rate Equations and Order of Reactions.mmap - 2005/1/31 -

 (Z) Collision
Frequency Vary only a little when the temperature change
(A)Arrhenius Constant (P) Orientation / geometrical Depending on the
/ probability factor nature of the reaction
The distribution is Simple Collision
temperature Maxwell-Boltzmann Theory (Effective
dependent distribution of Collision)
molecular speeds
The total area under the curve is independent of temperature.
i.e. the total no. of particles present Energy larger than
activation energy
Arrhenius Equation
An energy barrier the reactants need to overcome for the reaction to proceed.
Providing an By varying the temperature and measuring the rate of a reaction
alternative pathway A plot of ln k versus 1/T
with a different A plot of ln rate versus 1/T if
activation energy, initial rate method is used
usually lower. Effect of catalyst A plot of ln 1/t versus 1/T if constant
e.g iron in Harber process Activation Energy Determination of amount approach is adopted
By breaking up a single step into a multi-steps positive catalyst activation energy Repeat a reaction at two
reaction with lower activation energy different temperature
e.g. H+ in decomposition of H2O2 In the reaction k can be
negative catalyst
replaced by rate if initial rate
The catalyst has the same phase as the reactants and product method is used
k can be replaced by 1/t if constant
amount approach is adopted
e.g. a pentavalent transition
The Effect of state
homogeneous Temperature Change transition state (or
catalysis Catalysis and Catalyst on activated complex)
Reaction Rate can never be isolated
e.g.
acid-catalysed
esterification
The catalyst has a different phase as the reactants and product
Single stage reaction
heterogeneous Energy profile
catalysis
e.g. Catalytic
decomposition
of hydrogen
peroxide by
maganese(IV)
oxide
chemsorption / adsorption on the surface of the catalysis
Fe(s) Haber process
Pt(s) or V2O5(s) Contact process
e.g. carbocation
Ni(s), Pt(s) or Pd(s) hydrogenation of oil Multi-stage Reaction Reaction intermediate
Other examples can be isolated at low temperature
Ni(s) and NiO Gasification of naphtha in product of town gas
rate-determining step The step with the highest activation energy
Rh(s) and Pt(s) Catalytic Converter (r.d.s.)
The step with the lowest rate
zymase in the fermentation by yeast Enzymes
15. The Effect of Temperature Change and Catalyst on Reaction Rate.mmap - 21/5/2005 -
 A state where no macroscopic
change is observed.
Thermal dissociation of
calcium carbonate
At equilibrium and only at equilibrium, Esterification
All chemical equilibria are
the order of reaction with respect to a Action of acid and alkali on
dynamic in nature. i.e.
species will be the same as the bromine water
forward rate = backward rate Examples
stochiometric coefficient of the species Equilibrium Action of acid and alkaline on
potassium dichromate
including all species Generic equilibrium constant, K
Action of acid and alkali on
Equilibrium constant in terms bismuth chloride
Excluding those species having no of concentration, Kc Examples
effect on the equilibrium position e.g. The amounts of reactant and
solvent(species in large excess), Equilibrium constant in terms
product are usually not equal
insoluble solid/liquid of partial pressure, Kp
in an equilibrium.
Unit of equilibrium constant
The equilibrium concentrations of all species are determined by the
initial concentrations of them and the equilibrium concentration of
any one of them. Definition : a set of reactant and product concentration
Assuming that the rate of reaction is extremely slow Using of equilibrium constant and reaction quotient
and quenching is not required before any titration is to predict the direction to which the equilibrium
done. Esterification position will be shifted.
Q = K : the system is at equilibrium
Preparation of solutions with Reaction Quotient (Q)
known [Fe(NCS)]2+(aq) Construction of a Q > K : the equilibrium position will be shifted to the left
Equilibrium
concentration using excess calibration curve Q < K : the equilibrium position will be shifted to the right
Fe3+(aq) or NCS-(aq) Formation of Law
using colorimeter [Fe(NCS)]2+(aq)
Determination of Equilibrium The principle states that when a system in equilibrium is
Determination of the equilibrium concentration of complex subjected to a change, the system will response in a way so that
Equilibrium constant constants
[Fe(NCS)]2+(aq) using colorimeter and the calibration the effect of the change imposed will be minimized.
curve prepared Effect of change in concentration
Dynamic Equilibrium
Assuming that the rate of reaction is extremely by decreasing/increasing the volume
slow and quenching is not required before any by adding one of the product/reactant
titration is done Effect of change
in pressure this has no effect on
The titration is self-indicating if standard Reaction between Equilibrium the equilibrium
KCNS(aq) is used in the determination of the Fe2+(aq) and Ag+(aq) position by adding an inert gas position
concentration of Ag+(aq). The solution will turn
red at the end point with the formation of
Use of change in The rate of a reaction
blood red [Fe(NCS)]2+(aq) complex.
distribution of molecular with a higher
The value shows the relative amounts of products and reactants when speed to explain the activation energy is
Le Chatelier's
the system is at equilibrium i.e. extent of reaction at equilibrium. effect of change in more sensitive to the
principle
The value is depending on the temperature on the change in
relative stability of the equilibrium position. temperature
Significance of
products comparing with the Effect of
equilibrium constant
reactants change in
temperature
The value is temperature
dependent.
Catalyst has no effect on the equilibrium position.
It only shortens the time required for a system to
reach a state of equilibrium.
Effect of catalyst Catalyst does not change the relative stability of
the products comparing with the reactants
16. Dynamic Equilibrium.mmap - 6/4/2005 -
 acid : substance that produces
H+ in water
Arrhenius definition base : substance that produces
OH- ions in water
Different Bronsted Lowry acid : proton donor
definitions definition Introduction of the concept of
base : proton acceptor
conjugate acid-base pair
acid : electron acceptor
Lewis defintion
base : electron donor
An Arrhenius acid (base) must be a Bronsted Lowry acid (base) and a
A more negative pKa (pKb) value means a larger Ka (Kb) Bronsted Lowry acid must be a Lewis acid (base) but not vice versa.
value, thus a stronger acid (base).
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
Auto-ionization
Acidity and (dissociation) of
Basicity water A neutral
constants solution
HA- is relatively more stable has a pH 7
when comparing with H2A than only at
A2- when comparing with HA- Acid Base 25°C.
A2- has a much higher charge Equilibrium I :
density than HA- and has a very Basic Concepts
high potential energy i.e. more Ka1 is always much Successive
unstable larger than Ka2 ionization of
Originated from French "pouvoir hydrogene" (power of hydrogen).
It is more difficult to remove a polyprotic
positive proton from negative (polybasic) acid
HA-(aq) than from electrically
neutral H2A(aq) Every unit increase / decrease in pH scale means a ten-fold decrease / increase
Beside the small value of Ka2, the second step of the in the concentration of hydroxonium (H3O+) ion
ionization is also suppressed by the presence of H3O+ from
pH scale
the first step of dissociation which will tend to shift the
equilibrium position of the second step to the left. This is
using pH paper / universal indicator
known as common ion effect (of H3O+ in this case).
Eventually, the amount of H3O+ from the second step of Measurement of pH Need of calibration using a
ionization will be very minimal. Using pH meter buffer solution before use
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 -
 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).
phenolphthalein strong acid vs
or methyl orange strong alkali
Choosing of
strong acid vs indicator and
methyl orange weak alkali
pH titration Buffer solution
weak acid vs Curves
phenolphthalein strong alkali
no suitable weak acid vs
indicator weak alkali In the calculation of the pH of a buffer solution, it is
assumed that the inter-conversion between the acid
Acid-base (base) and its salt upon mixing is negligible.
Add phenolphthalein to the mixture, then
do the first part of the titration (V1).
Equilibrium II : The buffering capacity of a buffer solution is depending
Thereafter, add methyl orange and do the Buffers and on the concentrations of the acid/base and its salt.
second part of the titration (V2). Indicators
A mixture of Na2CO3 (V1+V2) Double Acid-base indicator is usually a weak acid (base) which
and NaHCO3 (V2) indicator colour is different from its conjugate base (acid).
A mixture of NaOH (V1) and titration Human eyes are only capable to detect a colour change
Na2CO3 (V1+V2) Examples when the concentration of one coloured substance is more
than 10 times of another coloured substance.
A mixture of NaOH (V1)
and NaHCO3 (V2)
Acid-base
indicators
18. Acid-base Equilibrium II.mmap - 21/5/2005 -
 reducing agent is
the reagent which Remember the Oxidation
is oxidized in a common strong half Addition of oxygen atom
redox reaction reducing agents equation Removal of hydrogen atom
By Combining Oxidation
Losing of electron
oxidizing agent is two half
the reagent equations Increase in oxidation no.
which is reduced Reduction
Remember the Removal of oxygen atom
in a redox half Definition
common strong Addition of hydrogen atom
reaction equation of redox
oxidizing agents Reduction
reaction Gaining of electron
The change in oxidation no. per atom is the same Decrease in oxidation no.
as the no. of electron being lost or gained by that A redox reaction in
particular atom which an element
Balancing
Figure out the no. of atom that will be oxidized and undergoes
the no. of atom that will be reduced by using the
Redox oxidation and
change in O.N. Equations Disproportionation reduction at the
reaction same time.
Add H2O to either side of the equation to get the By change in
number of O atom balanced if necessary. oxidation no.
Add H+ to either side of the equation to get the Redox Reactions no. of proton - no. of electron associated
number of H atom balanced if necessary.
with an atom assuming that all bonding
Check the presence of H+ or OH- on the both sides electrons are belonging to the more
to ensure it agrees with the acidity/alkalinity of electronegative atom
the medium used. Oxidation Rules of the sum of the oxidation no. of
For reactions in acidic medium, there should no. assigning all atoms in a species equals
be no OH- ion on the both sides of the oxidation the overall charge carried by
equation Check the the species.
number
medium of
For reactions in alkaline medium, there reaction
should be no H+ ion on both sides of the
equation
19. Redox Reactions.mmap - 2005/5/23 -
 Definition : The difference between the charge on an electrode and the
charge in the solution in which the electrode is immersed in.
Electrochemical series is constructed by arranging the standard electrode Practically, it is not possible to determine the absolute potential of a half cell. Therefore, for the
potentials measured in an ascending order. i.e. the most negative value first. sake of comparison, the electrode potential of standard hydrogen electrode is defined as 0 V.
The species on the left of the By convention, the reduction half equations are tabulated The value is depending on the activity of the electrons in the electrode
table are oxidizing agents. in the ECS. Therefore, standard electrode potential is also This value is also related to the nature, including concentration, of the
The species on the right of the known as standard reduction potential. electrolyte in which the electrode is immersed in.
table are reducing agents.
Electrode potential By definition, the electrode
Those oxidizing agents at the bottom of the list are strong oxidizing agents potential of an unknown half-cell
while those reducing agents at the top of the list are strong reducing agents. (of a half-cell) is the e.m.f. of an
The values list in an ECS are all measured at standard conditions electrochemical cell measured at
and all species involved are in their standard states. standard condition where a
standard hydrogen electrode By definition, overall e.m.f of a cell = E(right) - E(left).
An increase in concentration of an oxidzing agent will shift the
Concentration and (SHE) is used as the left-hand When hydrogen electrode is used as the left-hand electrode,
equilibrium position to the right and make the value more positive.
temperature electrode and the unknown E(right, the unknown electrode) = overall e.m.f. of the cell
An increase in concentration of a reducing agent will shift the Dependence on concentration dependence of electrode is used as the
equilibrium position to the left and make the value more negative. electrode potential right-hand electrode. The sign of the electrode potential of the unknown half cell
is the same as the polarity of the right hand electrode
The value is only depending on Electrochemical Series (unknown half cell) in the cell diagram.
Nernst Equation concentration (including partial pressure in
(Not required in HKAL syllabus) (ECS)
case of gas) and temperature, the size of
Q : reaction quotient the electrode has no effect on the value. The metal concerned will be used
as the electrode immersed in a In some cases, the solution will be saturated
Compare the strengths of oxidizing agents (or reducing agents) solution containing the salt of the with the salt and with some insoluble salt
metal. present.
A redox reaction with a Involving e.g. Cu(s) | CuSO4(aq) e.g. Ag(s)|AgCl(s)|Cl-(aq)
positive overall e.m.f. metal
will be energetically
feasible. An inert electrode, e.g. Pt, is immersed
To predict the energetic Use of
electrochemical in a mixture of the reduced and oxidized
The feasibility of a reaction is also depending on the feasibility of a redox
series forms of the reagent concerned. e.g. Pt(s) | Fe2+(aq) , Fe3+(aq)
kinetic stability (activation energy) of the system which is reaction Not involving e.g. Fe3+(aq) /Fe2+(aq) , I2(aq)/I-(aq)
not related to the overall e.m.f. determined. metal e.g. C(graphite) | 2I-(aq) , I2(aq)
e.g. disproportionation of Cu+(aq) in water
To ensure the overall e.m.f. of the cell be positive, Half
E(cell) = E(cathode) - E(anode) To predict the overall e.m.f. cell
= E(more positive) - E(less positive) of an electrochemical cell
Electrochemical Cells
A set of symbols are used to represent the set up of an electrochemical cell.
Platinized = covered with platinum black
Standard hydrogen electrode
Symbols = covered with platinum powder
used Pt(s) | H2(g) | 2H+(aq)
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. The electrodes of the two half cells are connected
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 together by an external wire.
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) IUPAC Cell Only KNO3 and NH4Cl are used in the salt
e.g. Zinc-carbon cell diagram bridge since the migration speed of the
cation and anion are similar and the voltage
The electrolytes of the two reading will not be affected.
Primary cell
half cell are connected The salt bridge is used to provide cations and
together by using a salt bridge. anions to balance the negative and positive
charge cumulated in the two half cells during
e.g. Lead acid accumulator the discharge of the cell.
Secondary cell Some
examples
Electrochemical cells The use of porous partition will create a
(rechargeable In some electrochemical cell,
cell) a porous partition is used to junction potential across the partition and
separate the two electrolytes the voltage measured will be different from
instead of using a salt bridge. the case if a salt bridge is used.
e.g. Hydrogen-oxygen fuel cell To measure the e.m.f. of a cell, the current
Fuel cell flowing through the external circuit should be
Measurement of e.m.f of an kept as minimal as possible.
electrochemical cells. Use a voltmeter with high impedance
Use a potentiometer
20. Electrochemical Cells.mmap - 9/5/2005 -
 Definition : region with identical properties.
Phase 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

Isotherms 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.
Ideal gas
The projection along
the temperature axis
(Isotherms)
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
As it is
difficult
PVT surface to study a
Ideal gas
3-dimensional 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.
surface,
the
projections
along the Phase diagram of The diagram is known as phase diagram.
volume water
axis and critical temp : above this temperature, gas cannot be compressed into liquid without cooling.
the AB : sublimation curve - conditions that solid and vapour can coexist at equilibrium.
temperature BC : vaporization / boiling curve - conditions that water and vapour can coexist at equilibrium.
axis are BD : fusion / melting curve - conditions that solid and liquid can coexist at equilibrium.
usually
studied B : triple point - the conditions that solid, liquid and vapor can coexist at equilibrium.
separately. Real substance BE : supercooling curve - the condition that a liquid exists at a temp. lower than its melting
e.g. water 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.

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

Special
features of Like most substances, the fusion curve of carbon dioxide has a positive
the phase slope. This implies that the melting point of carbon dioxide increases
diagram of with increasing pressure.
carbon The triple point pressure is higher than atmospheric pressure. This implies that dry ice will
dioxide 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
Special
rearrangement of atoms in solid state.
features of
the phase If graphite is heated to molten state and allowed to crystallize under high pressure,
diagram of artificial diamond can be made. Moreover, the crystallization is very fast comparing with
carbon the natural process of formation of diamond, the diamond crystal obtained will be small
and may not be suitable for making jewelry.

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


The components cannot be
separated by fractional
distillation completely.
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 -
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
Difference between be depending on P, T and X
1-component and For a 1-component system, the (saturated) vapour pressure
(mole fraction) which will
2-component systems (P) of a substance is a constant at a given temperature.
need a 4-dimensional space to
represent.
Positive
deviation
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.
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.
Extreme positive
deviation
(2 immiscible liquids)
Deviation from
Raoult's Law
(non-ideal solutions)
Phase Equilibrium II :
Two-Component System
Raoult's Law
The boiling point of an ideal solution varies linearly with the composition approximately.
Negative
deviation
Extreme negative
deviation
(a solution of
involatile solute)
 At equilibrium, the rates of diffusion of the solute between two
Partition of a solute between 2 immiscible solvents immiscible solvents in opposite directions are the same.
Partition Law - At a
given temp. and at a As the unit of concentration
Solvent Extraction state of equilibrium, will be canceled out in the
(between 2 immiscible the ratio of calculation, the unit can be
solvents) concentrations of a expressed in any unit and
solute in two partition coefficient will have
immiscible solvents is no unit eventually.
constant.
Most common organic solvent are lighter than water except chloroform(CHCl3), tetrachloromethane(CCl4) and
1,1,1-trichloroethane
If the density of the solvents are not known, when we say solute A
is partitioned between solvent B and C, it usually means
e.g. The partition law is not applicable to the case where ethanoic
The law is only application to the case if acid is partitioned between hexane and water as ethanoic acid exists
the solute has the same molecular as dimmer in hexane (non-polar solvent) and as monomer in water
structure in the two solvents. (polar solvent)
Partition of a solute 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.
between 2 phases e.g. the microscopic water film on the surface of the chromatography paper
Partition of a solution between a Stationery phase
e.g. silica gel on an aluminium foil
stationery phase and a mobile phase
Mobile phase e.g. different kind of solvent or mixture of solvents
Phase Equilibrium III :
Three-Component
Systems
Paper Chromatography
(between a stationery phase At a given temperature, with a
and a mobile phase) 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).
23. Phase Equilibrium III . Three-Component Systems.mmap - 2005/5/23 -