Chem

MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND
STOICHIOMETRY MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND STOICHIOMETRY MOLE
MOLE CONCEPT AND STOICHIOMETRY
Relative Isotopic Mass is the ratio of the mass of an atom of an isotope to 1/12 of the
mass of a C12 atom.
Relative Atomic Mass is the ratio of the average mass of an atom of an element to 1/12
of the mass of a C12 atom.
Ar = ( relative isotopic mass x relative abundance )
Relative Molecular Mass is the ratio of the average mass of a molecule to 1/12 of the
mass of a C12 atom.
Mr = ( Ar of all atoms present in one molecule )
Relative Formula Mass is the ratio of the average mass of a formula unit of an ionic
compound to 1/12 of the mass of a C12 atom.
Mr = ( Ar of all atoms present in one formula unit of ionic compound )
Combustion
1. The mixture is cooled to room temperature, H2O condenses. So, the volume of H2O is
neglected in calculations.
Left: CO2 Formed + O2 Unreacted
2. The leftover gaseous mixture is passed through a base which results in further
contraction. Acidic gas CO2 reacts with the base
Left: O2 unreacted
MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND
STOICHIOMETRY MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND STOICHIOMETRY MOLE
C1V1 = C2V2
REDOX
Oxidising Medium Product Reducing Medium Product

Agent Agent
(reduced) (Oxidised)
MnO42- Acidic Mn2+ Fe2+ Acidic/ Fe3+
Neutral
Neutral/ MnO2
alkaline I- Acidic/ I2
Neutral /
Cr2O72- Acidic Cr3+
alkaline
I2 Neutral I-
S2O32- Neutral S4O6a2-
IO3- Acidic I2
C2O42- acidic CO2
H2O2 Acidic H 2O
H2O2 Acidic O2
BALANCING REDOX
1. Identify the species oxidised/ reduced.
2. Balance all atoms other than O and H
3. Add H2O to appropriate side of the equations to balance the number of O atoms
4. Add H+ to appropriate side of equation to balance the number of H atoms
5. Add electrons to appropriate side of equation to balance the total charge
6. Equate the number of electrons for half-equations

ATOMIC STRUCTURE ATOMIC STRUCTURE ATOMIC STRUCTURE ATOMIC STRUCTURE ATOMIC STRUC
ATOMIC STRUCTURE
Behaviour of Subatomic Particles in an Electric Field
Positively charged particles are attracted towards the negative plate and negatively
charged particles are attracted towards the positive plate. Neutrons/ neutral particles
remain unaffected.
q - Charge
m - mass
Electron Orbitals
An orbital is a region of space in which there is a high probability of finding an electron.
Heisenberg Uncertainty Principle - position and momentum of an electron cannot be

determined with absolute position.
Electrons form a three dimensional wave function around the nucleus, electron cloud.
Quantum Shell and Quantum Numbers
Principal Quantum Number tells us about the distance between the quantum shell and the
energy level of the shell.
Energy increases as the distance from the nucleus increases ( i.e. becomes more unstable
at higher quantum shells).
When electrons gain energy or in an excited state, it can jump a quantum shell
(absorption). Electrons can also emit energy to jump to lower quantum shell. (emission).
Orbitals
Orbitals in a quantum shells show how the electrons move. (s,p,d,f)
There can only be 2 electrons per orbitals.
s orbitals - spherical in shape, larger as quantum number increases.
p orbitals - dumbbell in shape, at each quantum shell there are: px, py, pz
d orbitals - shapes too complicated, only at 3rd quantum shell and beyond, set of 5
orbitals
f orbitals - 7 sets of orbitals


ELECTRONIC CONFIGURATIONS
Each orbital can hold a maximum of 2 electrons

An electron is represented by a half arrow
Electrons must be in opposite spins
Every orbital must be singly occupied before any orbital

is doubly occupied
All electrons in singly occupied orbitals have the same spin
Electrons fill the low energy orbitals before they fill higher energy orbitals.
Note that 4s orbital is lower in energy than 3d. 4s orbitals should be filled up first before
3d.
For ions, electrons are removed/added from/to highest filled energy level.
When d-block elements form ions, 4s electrons are lost first.

Anomalies in Electronic Configuration
Chromium, Cr: [Ar] 3d5 4s1
Copper, Cu: [Ar] 3d104s1
Close energy levels of 3d and 4s allows rearrangement of electrons to achieve a

configuration of lower total energy.
Electron-electron repulsion is minimised by having 1 electron in 4s orbital.
Half filled/ Fully filled 3d subtle are stable due to symmetrical charge distribution
IONISATION ENERGIES
1st Ionisation Energy is the energy required to remove 1 mole of electrons from 1 mole
of gaseous atoms of the element to form 1 mole of singly positively charged gaseous ions.

2nd Ionisation Energy is the energy required to remove 1 mole of electrons from 1 mole
of unipositively charged gaseous ions of the element to form 1 mole of doubly positively
charged gaseous ions.

Factors affecting Ionisation Energy
Size of nuclear charge - Across a period, as the size of positive charge increases, the
electrostatic forces of attraction between the nucleus and the outermost electron increase.
More energy is required to remove the electron. Hence, a higher ionisation energy with
increasing nuclear charge.
Distance of the electron from the nucleus - Electrostatic forces of attraction between
the nucleus and the outermost electron decreases with increasing distance between them.
Less energy is required to remove the electron. Hence, lower ionisation energy with
increasing distance.
Shielding Effect - Electrostatic forces of attraction between the electron and the nucleus
decreases due to repulsion from inner electrons. As the number of inner electrons
increase, shielding effect increase and electrostatic forces of attraction decreases. Less
energy is required to remove the electron. Hence, lower ionisation energy with increasing
shielding effect. ( Across a period, Shielding effect is negligible )

Singly filled vs doubly filled - two electrons in the same orbital faces repulsion which
offsets the attraction of the nucleus. Electron in a doubly filled orbital is easier to remove
than an electron in a singly filled orbital.
Anomalies In Ionisation Energy
Be-B and Mg-Al
1st IE of B is lower than that of BE
Be: 1s2 2s2

B: 1s2 2s2 2p1
The 2p electron removed from B is in the higher energy 2p subshell + Increased distance
+ increased screening effect.
N-O and P-S
1st IE of O is lower than N
N: 1s2 2s2 2p3

O: 1s2 2s2 2p4
Repulsion between the pair electrons in the same 2p electrons
Ionisation Energies Across Transition Metals
Across transition metals, 1st IE remains almost the same because electron to be removed
are from the same subshell (4s). The increase in nuclear charge (proton) is offset by the
increase in shielding effect due to the increase in inner electrons (3d). With the exception,
Cu: [Ar] 3d104s1

Zn: [Ar] 3d104s2
The Shielding Effect is the same, and electron is removed from the same subshell.
However, Zinc has a greater nuclear charge. The repulsion between the pair of electrons
in 4s orbital is not enough to offset the increase in nuclear charge.
Successive IE are larger as electrons are removed,

nuclear charge remains the same
Remaining electrons are more strongly attracted to the nucleus
Large jump in IE of an atom tells us the

number of valence electrons
Change in quantum shell
CHEMICAL BONDING CHEMICAL BONDING CHEMICAL BONDING CHEMICAL BONDING CHEMICAL BON
CHEMICAL BONDING
Covalent Bonding
Most stable situation between two covalent bond is when the attraction between electrons
and nucleus are just balanced by the electron-electron and nucleus-nucleus repulsions.
Electrons are shared between the 2 adjacent atoms and has the highest electron density
on the axis that joins them.
For 2nd Row elements, an atom can only accommodate up to 8 electrons because they
only have 4 orbitals in their valence shell ( 2s, 2px, 2py, 2pz ).

For 3rd Row elements, atoms can promote their electrons to d-orbitals to form more than 4
covalent bonds. (hybridisation). This is possible because energy released when bonds
formed is greater than the energy absorbed to promote.
Dative Bond
In dative bond, one atom provides both bonding electrons in a covalent bond.
NH3 and BF3 :
NH4Cl :
CO :
HNO3 :
Hydrated Ions:
Valence-Shell Electron-Pair Repulsion Theory
Covalent molecules possess a definite, unique, three-dimensional shape which is

determined by the angles between the bonds within them. In turn, the bond angles are
determined by the arrangement of the electrons around each atom. These electron pairs
(bp and lp) behaves as if they repel one another to be as far as possible from each other.
Working out the shape of molecules

Orbitals with lone pairs are larger and closer to
the nucleus, and occupy larger space around the
1. Count the number of bonds
central atom. Greater repulsion. Hence,
2. Count the number of lone pairs
3. Deduce the hybridisation. LP-LP > LP-BP > BP-BP
If you have more than 4 electron pairs about the central atom, ignore repulsions at angles
greater than 90
Explain the arrangement of ClF3

Treat double bonds as single bond, a double bond has one bond and one bond.
Hybridisation
Hybridisation accounts for the bond shape so that the bond angles and the the bonds are
coherent.
For example, after promoting its electrons, methane should provide bond angles of 90.
However, a tetrahedron of 109.5 is observed. Hence, Carbon must have hybridised to
give hybrid orbitals pointing at 109.5. Energy is absorbed to promote electrons to form
hybrid orbitals.
Bonding with Orbitals
Overlap of s or/and p orbitals causes area of electron density to be in between the 2

bonded atoms. The resulting bond is called bond.
2p orbitals can also overlap sideways to form a bond. It is not possible to bond with only
bond.
Double bond consists of a bond and a bond.
Triple bond bond has 2 bond and 1 bond

Electronegativity
Electronegativity is the ability of an atom in a molecule to attract a bonding pair of

electrons to it.
N, O, F are the most electronegative.
1. 2 molecules similar in electronegativity results in a pure covalent bond

2. 2 molecules with differences in electronegativity results in polar covalent bond
3. 2 molecules with large differences in electronegativity results in ionic bond
Electronegativity Trends
Electronegativity is affected by: Number of Protons, Distance from nucleus, Screening
So, across a period, electronegativity increases as the number of protons increase and
hence attracts the bonding pair of electrons strongly.
And, down a group, electronegativity decreases as the bonding pair is shielded by the
electrons and getting further away from the nucleus. Hence , weaker attraction between
the nucleus and the bonding pair.
Dipoles
The drift of electrons result in separation of charges, known as dipoles. The overall dipole
of the molecule is determined by its shape and bonds.
Polarising Ability
The ability to pull back electrons. Explains why some ionic bonds have covalent
character. Cations polarises anion.
AlCl3 is ionic. However, because Al is

highly positively charged (3+) and has
a small radius. It has a very high charge
density. This pulls back the electrons such
that the ionic bonds have covalent characteristics

However, because Cl is electronegative, the bond will be polar.
Intermolecular Forces
All intermolecular forces are electrostatic.
permanent dipole-permanent dipole forces
Polar molecules will have permanent dipoles. Positive region of polar molecules attract the
negative region of another. Strength of pd-pd increases as dipole moment increases.
London Dispersion Forces
At an instant, there may be an instantaneous dipole moment due to movement of

electrons. This induces a dipole on another atom/ molecule. Temporary dipoles causes
atoms to be attracted to one another.
The dispersion forces gets stronger with increasing polarisability. Covalent substances
with large Mr and volume have stronger dispersion forces.
London dispersion forces occurs all the time
Hydrogen Bonding
Hydrogen bonded to very electronegative molecule > hydrogen almost a bare proton
This attracts the lone pairs of adjacent molecules.
Strength of hydrogen bonds are strongest when atoms are collinear.
Water can form an average of 2 hydrogen bonds per molecule. Stronger forces of
attraction between water molecules > higher mo/bp for water
These hydrogen bonds:
- form a lattice across the surface of water > high surface tension
- ice bonds tetrahedrally to produce an open lattice with a lot of open spaces. More space
per unit mass > lower density.
Molecular Lattices
Silicon, SiO2, BN, Diamond, Graphite etc
- High mp/bp - breaking covalent bond throughout the structure

- electrical insulators except graphite
Explaining conductivity of Graphite
Each Carbon atom is hybridised to form sp2 orbitals. The leftover p orbital with one
electron overlap to form a pi above and below the sheet of graphene. They are delocalised
electrons that are free to move.
Direction of electron travel is along the layers - not from one sheet to another.
The instantaneous dipole between grapheme sheets due to delocalised electrons hold the
layers together.
The dispersion forces between the layers are weak and allow the layers to slide over one
another easily.


Ionic Bonding
Metal atoms with low ionisation energies usually lose all their valence electrons
There is no such thing as 100% ionic bond. If an anion is highly polarisable due to the
small, highly charged cation, there is an increase in electron density between the ions and
increase the degree of covalent bonding.
To determine the covalent characteristics,
Polarisability of anion
Charge Density of Cation (polarising power)
Co-ordinate numbers
NaCl is 6:6 co-ordianted. This means that around an ion in a giant ionic structure, there
are 6 other ions around the ion. The co-ordinate numbers represents the maximum
number of ions around a central ion before there is repulsion which makes the giant ionic
structure less stable.
vs
CsCl is 8:8 co-ordinated. 8 other ions around a central ion. Cs ion can have more ions
around it because Cs is larger than Sodium.
mp/bp
Lattice energy
Strength and brittleness
With small amounts of stress, ions of similar charges are forced together, the lattice resists
this strongly > strong
Strong force > shatters and breaks down catastrophically > brittle.
electrical conductivity
In molten or aq, individual ions have net overall electrical charge and are free to move
around. electric current can flow
Metallic Bonding
Metallic bonding is described as an array of positive ions in a sea of delocalised electrons.
The valence orbital overlaps with the corresponding valence orbital to form a molecular
orbital. The electrons can move freely in these orbitals and are said to be delocalised.
The metal is held together by the strong electrostatic forces of attraction between the
positive nuclei and the delocalised electrons.
Strength of Metallic bond
Transition metals can involve 4s electrons and 3d electrons. Stronger electrostatic forces
of attraction and hence, higher mp/bp.
Electrons will move towards the positive end when there is a potential difference. >
electrical conductivity.
While they are all positively charged, the electrons shields the positive charge from
repulsion when force is applied. > malleable and ductile.
Lustrous and shiny - When a photon of light hits the surface of the metal, electrons on the
metals surface oscillates. Photons bounce off surface without any loss of momentum.
= nRT pV= nRT pV= nRT pV= nRT pV= nRT pV= nRT pV= nRT pV= nRT pV= nRT pV= nRT pV= nRT pV= nR
pV = nRT summarises Boyles Law, Charless Law, Avogadros Law.
p - Pressure in Pa (1 atm = 1.01 x 105 Pa, 1 bar = 105 Pa)
V - Volume in m3
n - mol.
R - 8.31 J K-1 mol-1
T - in kelvins
Law of Partial Pressures
Ptotal = p i (total pressure = sum of partial pressure components)

Kinetic Molecular Theory of Gases
4 assumptions for ideal gases:
- Gas molecules are rigid spheres

- No IMF between gas molecules
- Perfectly elastic collision between gas molecules
- Gas molecules have no volume, point mass
Real Gases
@ High pressure,
- Volume of gas is low

- Volume of gas molecules is now
significant compared to the total
volume of the gas > deviates from
ideality
@ Low temperature
- Volume of gas is low

- Volume of gas significant in
comparison to the total
volume of the gas
Gas possess less KE

- Travel slowly and collide with less
force
- IMF significant for slow molecules >
inelastic collision
@ Strong IMF,
Differences in IMF, Gas molecules with stronger IMF deviates more from ideality.
ERMOCHEMISTRY AND THERMODYNAMICS THERMOCHEMISTRY AND THERMODYNAMICS THERMOCH
D THERMODYNAMICS THERMOCHEMISTRY AND THERMODYNAMICS THERMOCHEMISTRY AND
Definitions
Standard enthalpy change of reaction, Hr

- Enthalpy change which occurs when molar quantities of reactants react to Standard Conditions
form products under standard conditions
- 298 K, 25 C
- 1 bar
Standard enthalpy change of formation, Hf - 1 mol/dm3
- Enthalpy change which occurs when 1 mole of compound is formed from its
constituent elements in their standard state, under standard conditions.
Standard enthalpy change of combustion, Hc ( -ve, per mol of substance burned)

- Enthalpy change which occurs when 1 mole of substance is burned completely in
excess oxygen,, under standard state and conditions.
Standard enthalpy change of neutralisation, Hneut ( -ve, per mol of water formed,
-57kJ/mol)
- Enthalpy change when 1 mole of an acid and 1 mol of an alkali react to form 1 mole of
water under standard state and conditions.
Standard enthalpy change of atomisation, Hat (+ve)

- 1 mole of gases atoms is formed from the element, all in their standard states and
conditions.
Bond Energy (+ve)

- 1 mole of a bond is broken to give separated atoms, everything being in gaseous state
Lattice Energy, Hlatt (-ve)

- 1 mole of an ionic compound is formed from its constituent gaseous ions, under
standard states and conditions
Ionisation Energy (+ve)

- 1st IE: 1 mole of gaseous atoms each loses an electron to form 1 mole of unipositive
gaseous ions
Electron Affinity (1st: -ve, 2nd: +ve)

- 1st EA: 1 mole of gaseous atoms each acquire an electron to form 1 mole of gaseous
uninegative ions
Standard enthalpy change of hydration, Hhyd (-ve, q/r)

- 1 mole of gaseous ions dissolve in sufficient water to give an infinitely dilute solution
Standard enthalpy change of solution, Hsoln

- 1 mole of an ionic substance dissolves in water to give a solution of infinite dilution.
Thermochem
Heat evolved or absorbed at constant pressure, q=mc

exothermic
endothermic
G = H - TS
Spontaneous/ Feasible
- one that takes place naturally in the direction stated without a need for continuous input
of energy from the outside system
Entropy, S
Randomness or disorder in a system, reflected in the number of ways the energy in a
system can be distributed through the motion of its particles.
increase in entropy a system becomes more stable when its energy is spread out in a
more disordered state
Temperature
With an increase in temperature, the average kinetic energy of the particles an the range
of energies increases > more ways to disperse the energy among the particles.
Change in Phase
Lowest entropy - solid, vibrating about fixed position, entropy increases with increasing KE
Change from solid to liquid to gas, the particles have more range of motion and disorder,
as well as more ways to distribute their energies.
Change in number of particles for gaseous species/ Change in pressure
The number of particles increase, number of ways that energy and particles can be
distributed increases.
Dissolution of ionic solid
- entropy increases because ions are free to move in solution

- entropy decreases water molecules motions are restricted as they arrange around an
ion
Gibbs Free Energy, G
G < 0 > reaction is feasible and takes place spontaneously.

- exergonic
G = 0 at equilibrium. i.e. phase change
G > 0 > reaction not feasible and does not take place spontaneously
- endergonic
G = H - TS can be plot into a linear graph

Chem

Transféré par

Informations du document

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Chem

Transféré par

Droits d'auteur :

Formats disponibles

MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND STOICHIOMETRY MOLE CONCEPT AND

MOLE CONCEPT AND STOICHIOMETRY

Oxidising Medium Product Reducing Medium Product

1. Identify the species oxidised/ reduced.

2. Balance all atoms other than O and H

4. Add H+ to appropriate side of equation to balance the number of H atoms

5. Add electrons to appropriate side of equation to balance the total charge

6. Equate the number of electrons for half-equations

Behaviour of Subatomic Particles in an Electric Field

An orbital is a region of space in which there is a high probability of finding an electron.

Heisenberg Uncertainty Principle - position and momentum of an electron cannot be

Quantum Shell and Quantum Numbers

Orbitals in a quantum shells show how the electrons move. (s,p,d,f)

There can only be 2 electrons per orbitals.

s orbitals - spherical in shape, larger as quantum number increases.

f orbitals - 7 sets of orbitals

Each orbital can hold a maximum of 2 electrons

Every orbital must be singly occupied before any orbital

When d-block elements form ions, 4s electrons are lost first.

Anomalies in Electronic Configuration

Chromium, Cr: [Ar] 3d5 4s1

Copper, Cu: [Ar] 3d104s1

Close energy levels of 3d and 4s allows rearrangement of electrons to achieve a

Electron-electron repulsion is minimised by having 1 electron in 4s orbital.

Factors affecting Ionisation Energy

Anomalies In Ionisation Energy

Be-B and Mg-Al

1st IE of B is lower than that of BE

Be: 1s2 2s2

N-O and P-S

1st IE of O is lower than N

N: 1s2 2s2 2p3

Repulsion between the pair electrons in the same 2p electrons

Ionisation Energies Across Transition Metals

Cu: [Ar] 3d104s1

Successive IE are larger as electrons are removed,

Large jump in IE of an atom tells us the

NH3 and BF3 :

Valence-Shell Electron-Pair Repulsion Theory

Covalent molecules possess a definite, unique, three-dimensional shape which is

Working out the shape of molecules

Explain the arrangement of ClF3

Bonding with Orbitals

Overlap of s or/and p orbitals causes area of electron density to be in between the 2

Double bond consists of a bond and a bond.

Triple bond bond has 2 bond and 1 bond

Electronegativity is the ability of an atom in a molecule to attract a bonding pair of

N, O, F are the most electronegative.

1. 2 molecules similar in electronegativity results in a pure covalent bond

Electronegativity is affected by: Number of Protons, Distance from nucleus, Screening

AlCl3 is ionic. However, because Al is

All intermolecular forces are electrostatic.

permanent dipole-permanent dipole forces

London Dispersion Forces

At an instant, there may be an instantaneous dipole moment due to movement of

London dispersion forces occurs all the time

This attracts the lone pairs of adjacent molecules.

Strength of hydrogen bonds are strongest when atoms are collinear.

These hydrogen bonds:

Silicon, SiO2, BN, Diamond, Graphite etc

- High mp/bp - breaking covalent bond throughout the structure

Explaining conductivity of Graphite

To determine the covalent characteristics,

Strength and brittleness