Foundational Topics / Inorganic Chemistry

Chapter 1 – Atomic Structure and Physical Periodicity

(for this chapter specifically, there’s a lot of additional background & very basic info, so the
key stuff is highlighted)

 Atoms have 3 components – Protons, Neutrons and Electrons

o Protons and Neutrons are also known as “nucleons”
o Protons and neutrons are found in a nucleus (a very concentrated and dense
ball of stuff in the centre of the
atom), surrounded by electrons
 Info on Nucleons:

Name Proton Electron Neutron

Mass 1 1/1836 1
Charge +1 -1 0
 TLDR: mass of proton = mass of neutron
| charge of 1 proton cancels the charge of
1 electron
 Chemical Symbols:
o nucleon number = number of
protons. This is at the bottom.
This will tell you what element
you are looking at.
o Ar = atomic mass number (the bigger number). This will tell you what isotope
you are looking at. This is the sum of the number of protons and neutrons in
the atom.
o The symbol in the middle is just the symbol for the element :)
o E.g. 136C is the carbon-13 isotope
o Using the number of protons and the charge of an atom, you can find out the
number of electrons
 So … what’s an isotope?
o Same number of protons, and electronic configuration, with different number
of neutrons
o Isotopes may be unstable (like carbon-13)
 Ions
o Ions are charged (either more protons/electrons than the other)
o Cation is positive, anion is negative
 Deflection of ions
o Cations deflect towards the negative plate, anions deflect to the positive plate
(opposite charges attract)
o angle of deflection may be deduced as follows:
 q
θdeflection ∝
, where q is the atom's charge and m is its mass
m
 On the topic of mass …
o Relative atomic mass is the mass of the AVERAGE mass of an atom relative
to 1/12th of the mass of a carbon-12 atom
o Relative isotopic mass is the mass of an isotope relative to 1/12th the mass of a
carbon-12 atom
o Average mass on an element (the one given in your data booklet)/isotopic
abundance is:

relative mass of ( element )=∑ (mass of isotope)(%abundance)

o Taking chlorine as an example: chlorine 35 and 37 are found in a 3:1 ratio.

Therefore:
Ar Cl=( 35 )( 75 % ) + ( 37 ) ( 25 % )=35.5

 The Quantum Shell

o (as quantum physics suggests) the energy levels of electrons can be described
with numbers called quantum numbers | just think of them as levels, n =
1,2,3,4 …
o The max number of electrons that can go into each shell is 2n
 Subshells
o Each shell can be divided into further subshells
o For n = 1 to 4 at least, when you go up a shell, you add an extra type of orbital
i.e. number of subshell types = the value of n

Quantum number, n Types of subshells notation

1 s 1s
2 s/p 2s / 2p
3 s/p/d 3s / 3p / 3d
4 s/p/d/f 4s / 4p / 4d / 4f
 Orbitals
o Heisenberg Uncertainty Principle, Schrödinger’s Wave Equation Ψ aside: An
orbital is a region of space with a 90% probability of finding an electron.
o If an orbital does not contain any electrons, it is called degenerate.
o S-subshell: The s-orbital is a literal sphere, with no nodal plane/point with no
area (NOTE this actually isn’t true, there are nodal planes but that is … not in
syllabus) | there is only 1 shape of s-orbital, the SIZE gets larger with a higher
energy level.
o P-subshell: The p-orbital is shaped like a dumbbell, and for the same “energy
level” n, they have the SAME SIZE (important for drawing orbitals) but
different orientations along the x, y and z axes | in other words, there are 3 p
orbitals for each 2p/3 etc. level
 o D-subshell: the d-orbitals have weird and funny shapes. | There are five d
orbitals in total.
 Orbital shapes :)

 The rules of Electronic Configuration

o Aufbau’s Rule: Orbitals with lowest energy are filled first, then move up from
there | vice versa, electrons are removed from highest energy orbitals first
o IMPORTANT TO NOTE FOR EXAM PURPOSES: because this is the H2
syllabus, the 4s orbital is filled first, but electrons are also removed from the
4s orbitals first

o Hund’s Rule: Degenerate orbitals must be all have 1 electron before an orbital
will have 2 orbitals
 The analogy is: on a bus, you would rather sit in an empty row of those
2 seat thingies that next to another person
o Pauli Exclusion Principle: If an orbital has two electrons,
they must have opposite spins (represented with 2 arrows in
opposite directions)
 Application: Electronic Configuration
 o 1s2 2s2 2p6 3s2 3p6 3d10 4s2 …
o The superscript (power) represents the number of electrons in that subshell
[you need to find the number of electrons and split them up to get the correct
orbital to stop at etc.]
o Note, the number of electrons in an atoms is basically your proton number.
o This will apply to cations and anions as well, just remove/add electrons
respectively as per the three rules above
o EXCEPTIONS: Chromium and Copper
 Cr: 1s2 2s2 2p6 3s2 3p6 3d5 4s1 (NOT 3d4 4s2)
 Cu: 1s2 2s2 2p6 3s2 3p6 3d10 4s1 (NOT 3d9 4s2)
 Why? Having a fully filled/half filled d subshell is more stable + the 3d
and 4s subshells have very similar energy levels, the chemistry
between those two is very weird :(
o “Blocks” in your Periodic Table

o A transition metal is a d-block element that forms one or more stable ions with
a partially filled d-subshell. | FRIENDLY REMINDER AGAIN, THAT
ELECTRONS ARE REMOVED FROM THE 4s SUBSHELL FIRST!!!
 The three besties when writing answers for periodic trends:
o Number of quantum shells determines distance of outer electron from the
nucleus | greater distance, weaker attraction
o Effective Nuclear Charge (knows as Zeff) combines:
 Nuclear Charge Z (dependent on number of protons)
 Shielding effect S: presence of inner-shell electrons repel outer shell
electrons, reducing net electrostatic force of attraction between outer
electrons and nucleus.
 Zeff = Z – S
 Trend in Atomic Radius
o Increases down the group
 Number of quantum shells increases
 Outer electrons further away
 As both nuclear charge and shielding effect both increase down a
group, the effective nuclear charge stays relatively constant
o Decreases across a period (except for noble gases, because their “atomic
radius” is a different type of atomic radius, cannot be used for comparison)
 Number of quantum shells the same
  Nuclear charge increases (more protons)
 Shielding effect remains relatively constant
 Outermost electrons are attracted more strongly and pulled closer to
the nucleus
o Ionic radius
 Note that in a period, the cations are isoelectronic with each other (and
so are the anions with each other), so shielding effect is THE SAME
 From cations to anions, the atomic radius will increase as the anions
have an extra quantum shell
 Beyond that, it’s business as usual with atomic radius decreasing down
the group
 Trends in Ionisation Energy (definition in chapter 5)
o Across the same atom, it will increase
 Effective nuclear charge will increase as electrons are lost
 Reduced shielding effect
 Also harder to remove a negatively charged electron from a positively
charged atom
 A small shift indicates a change in subshell (e.g. p -> s electron)
 A large shift indicates a change in quantum shell
 The number of electrons lost BEFORE the big change shows the
number of electrons in the outer shell (because the very large IE value
comes from the inner shell)
o Decreases down the group
 More quantum shells, electron is further from the nucleus –> weaker
electrostatic forces of attraction
 Both nuclear charge and shielding effect will increase down the group
-> effective nuclear charge will remain relatively constant
o Increases across a period
 Nuclear charge increases, shielding effect relatively constant ->
effective nuclear charge increases
o ANOMALIES!
 S has lower first IE than P, because of inter-electronic repulsion in the
full filled 3p orbital of P (think: 1s2 2s2 2p6 3s2 3p4)
 IE remains relatively constant across transition elements:
 Electrons are filled into 3d subshell, shielding effect increases
 Nuclear charge also increases
 Effective nuclear charge remains relatively constant
 Electrons are removed from the 4s subshell in transition
elements (i.e. the number of quantum shells are the same)
Chapter 2 – Chemical Bonding
 Note that all chemical bonds are electrostatic in nature.
 Summary of the types of chemical bonds/interactions:
o Ionic
o Covalent
o Metallic
o Hydrogen Bonding
o Permanent dipole – permanent dipole (pd-pd)
o Permanent dipole – induced dipole (pd-id)
o Induced dipole - induced dipole (id-id), known as Van der Waals’ dispersion
forces
 Note: you break bonds but overcome intermolecular forces!
 Electronegativity: the measure of an atom’s ability to attract the electrons in a
covalent bond towards itself
o Increases across the group
o Decreases down the period
 [think: your Zeff and number of quantum shell stuff, this is just like
I.E.]
o The “Big 7” of electronegative atoms: N/O/F/Cl/Br/I [with F being the most
EN]
o similar EN -> electron sharing -> covalent bonding
o large EN difference -> electron transfer -> ionic bonding
 Metallic Bonding
o What is it? [Giant ionic]
 Giant metallic lattice comprising of
 Regularly arranged metal cations surrounded by
 Sea of delocalised electrons
 Strong electrostatic forces of attraction between positively charged
metal cations and negatively charged electrons
o Drawing metallic bonding:

if you’d like, put in a legend as well

o Note for metallic bonding, the metal must be neutral! [in other words, your
number of electrons, charge and number of cation must match up]
 E.g. in the case of calcium, one Ca2+ cation must have two e-
accompanying it!
o Properties of metallic bonds
  (generally) high melting & boiling point
 Mercury and gallium exist as exceptions :(
 Strong electrostatic forces of attraction between …
 [if comparing between metals] bond strength is dependent on
charge density of the metal cation
 more energy required to overcome … bond
ionic charge
 charge density ∝
ionic radius
 Good electrical & thermal conductivity
 mobile charge carriers in the form of sea of delocalised
electrons
 Malleable & ductile (tl:dr it can be compressed & stretched)
 Layers of metal cations can slide over each other
 sea of delocalised electrons still will hold the metal cations in
place
 Hardness
 note metals are usually hard
 EXCEPTION: Group 1 and 2 metals are soft
 Ionic Bonding
o What is it?
 Giant Ionic Lattice
 Lattice of cations and anions
 held together by strong electrostatic forces of atraction
o Drawing ionic lattices
 it is what it is …

o Properties of ionic compounds

 high melting/boiling point due to strong electrostatic forces of
attraction between …
q−¿
 [if comparing] it’s about Lattice Energy |LE|∝ |q + ¿|
r +¿+ r ¿ ¿
−¿

 high LE = stronger bonds = more energy required to overcome bonds

 o Electrical conductivity
 [in solid state] ions are in fixed positions and are not free to move
 [in molten/aqueous state] the ions can act as mobile charge carriers
 the more concentrated an aq. solution, the higher the electrical
conductivity
o Hard and rigid, but brittle
 FYI the line where the lattice is broken is knows as the “cleavage
plane”

 Nature of Covalent Bonds

o Formed by the overlapping of two atomic orbitals
o Two types of covalent bonds: sigma (σ) and pi (π)
 Sigma bonds are formed by head-on overlap
 Pi bonds are formed by side-on overlap
 Note that d orbitals can effectively “behave as fancier p-orbitals” and
have σ/π bonding as well
o Comparing the strength of σ VS π bonds
 Side-on overlap is poorer than head-on overlap
  Hence π bonds are weaker than σ bonds
o Finding number of σ/π bonds
 The first bond between atoms will be σ
 Any further bonds after that are all π
o [FYI] Delta bonds
 Occur when 4 d-orbital
lobes have side-on overlap

 Comparing the strength of covalent

bonds
o (mentioned in energetics) Bond energy is the energy required to break 1 mole
of covalent bonds
o What is important for us here is that the magnitude of bond energy is a
representation of the strength of a given covalent bond/interaction
o In general, bond energy depends on the degree of orbital overlap, and how
strongly the electrons are attracted to the nuclei
o Two factors affecting bond energy
 Bond Length – distance between nuclei of two bonded atoms
 Smaller atoms form shorter and stronger bonds, and there is
more effective orbital overlap
 Conversely, longer bonds are weaker
 e.g. BE(C – F) > BE (C – I)
 EXCEPTION: BE (F2) < BE (Cl2) despite F being smaller than
Cl as despite F-F being shorter, the close proximity of the lone
pairs on F causes repulsion & hence bond strain
 Bond order i.e. number of covalent bonds
 More bonds between two atoms -> more electrons are shared ->
greater attraction between the nuclei and shared electrons ->
stronger bond -> higher BE
 However, the addition of the second bond will not be twice the
original value as bond #1 is sigma, bond #2 is pi -> the second
bond has less effective orbital overlap than the first -> it
contributes less to the BE value
 e.g. BE (C – C) is +350kJmol-1 , BE (C=C) is +610 kJmol-1 <
350 x 2
 Good (and important!) info to know: Bond Length, Covalent Radius, Van Der Waals’
Radius
o certain molecules (i.e. noble gases) only has VDW radii as they exist as
monoatomic gases i.e. no covalent bonding
 Lewis structures & dot-and-cross diagrams
o Ionic Compounds: How to draw?

 Remember that ionic bonding involves ions & the transfer of electrons
 The cation will just be the chemical symbol and the respective charge
 Charge is put outside a square bracket
  The anion will have (symbol) as its own valence electrons and (another
symbol) as the valence electrons
 For distributing the valence electrons around the anion:
 Application of Hund’s “bus seats” rule: You need to go around
the atom with valence electrons -> in other words, the accepted
electrons CANNOT be next to each other
 This sometimes will mean that there’ll be a lone electron on
one side, leave it be
o Covalent Compounds: TBH Lewis and dot-and-cross diagrams are rather
interchangeable for these
 Helps to start by drawing the Lewis structure first before throwing
1001 dots/crosses all over the place
 Choose the central atom; often of the lowest EN
 If there are negative charges, put it on the EN element
 If there are positive charges, put it on the less EN element
 Write a square bracket with a superscript for the charge [like this]+ (if
applicable)
 Make the terminal atoms achieve octet by adding single/double/triple
bonds
 Valency (number of additional electrons required per element
to achieve octet) very helpful here
 e.g Carbon has a valency of 4
 Account for non-bonding electrons in the central atom – VERY
important for geometry!!! [there’ll be example of Lewis structures in
VSEPR]
 Dative bonds:
 If the central atom cannot expand octet (Period 2) change a
double bond to a dative bond (represented by arrow)
 [for dot and cross] Draw out the remaining valence electrons using
Hund’s rule
 VSEPR Geometry
o Electron pairs arrange themselves are far apart as possible to reduce repulsion
o Lone pairs should generally be as far apart as possible
o Lone Pair – LP repulsion > LP – Bond Pair > BP – BP
o Deducing structure:
 See number of electron domains (bond pair/lone pair/double or triple
bond)(all counted as one each)
 [See table below]
 If more than 1 central atom exists, we state the shape (and
hybridisation state) with respect to the atom
e.g. trigonal planar sp2 hybridised carbonyl carbon
o Patterns:
 Angle of trigonal pyramidal < Angle of tetrahedral because BP – LP
repulsion is greater
  Ceteris paribus, bond angle of a more electronegative central atom will
be greater (applies to non-spherical geometries only)
 E.G. H2O vs H2S
Bond pairs are closer to the EN atom in O
Greater BP – BP repulsion, greater bond angle
 NOTE this doesn’t work for spherical geometries:
If you compare between CCl4 vs SiCl4, because the repulsions,
while different across compounds, are identical across a single
compound -> bond angle still 109.5º
 Larger terminal atom -> increases steric hindrance (BP - BP repulsion)
 Hybridisation
o Remember that is the GEOMETRY of the molecules that allows us to deduce
the hybridisation state and NOT!!! the other way around
o Required to explain non-“boxy” geometries (because p orbitals are
perpendicular to each other) + accounting for number of bonds formed
o Geometry: H2O has a bond angle of 104.5º but the 2 orbitals in unhybridised O
are p orbitals [giving bond angle of 90º]
o Number of bonds formed: Carbon is 1s2 2s2 2p2
o That leaves 2 singly filled orbitals to form bonds, but CH4 has 4 C – H
bonds???
o s & p orbitals mix to form new orbitals called hybrid orbitals

o Naming the hybrid orbitals:

 Number of electron domains n -> spn-1 hybrid
 unhybridized p orbitals form your π double/triple bonds
 For triple bonds, the 2 π bonds are PERPENDICULAR to each other,
e.g. ethyne C2H2:
 o s & p character
 sp3/2/1 tells you how many component orbitals were used to form the
hybrid
 hence sp3 will have 25% s character and so on
 sp orbitals are less elongated -> greater extent of orbital overlap
 hence sp orbitals form stronger bonds

 Covalent and Ionic Character

o Ionic & covalent character lies on a spectrum, with ionic bonding being 100%
electron transfer and covalent being 100% even sharing of electrons
o high EN difference between atoms -> increased ionic character
o Polarity of covalent bonds
 If no EN difference, bonding electrons shared equally
  If EN difference, there will be a charge separation (dipole), represented
by a dipole moment

o Polarisability of ionic bonds

 Ideal ionic bonding – nucleus of each ion only attracts its own
electrons
 In many cases the cation attracts the anion’s electrions causing a
distortion of the electron cloud

o Factors affecting degree of covalent character

 Polarising power caused by high cation charge density (high charge,
relatively small ionic radius)
 Polarisability caused by large anions (eg I-)
 Polarity of molecules ft. Dipole Moments
o If net dipole = 0, molecule is non-polar
 INTRAmolecular forces of attraction
o So far we have covered INTRAmolecular forces of attraction (between atoms
in a molecule), now it’s time to discuss INTERmolecular forces of attraction
BETWEEN molecules
o Instantaneous dipole-induced dipole forces
 Exists between all molecules
 (generally the weakest) form of inter-molecular force of attraction
 Strength depends on number of electrons in molecule (more
polarisable)
 Surface area of contact between adjacent molecules
o Permanent dipole – permanent dipole attractions
 Occurs in polar molecules between oppositely charged ends
 Moderately strong

o Hydrogen Bonding
 Stronger than both id-id & pd-pd
 Occurs when H is bonded to N/O/F
 EN atom pulls bond pair electrons to itself, creating highly electron
deficient H atom
 There must be an atom with a lone pair of electrons (like N/O/F)
 Drawing:
 Must have partial charges δ+ and δ-
 Draw the lone pair of electrons involved
 Label the H-bond
 Factors affecting H-bonding:
 Higher the EN of atom, more polarisation
of bond, stronger bonding
 Extent of H-bonding: depends on number of H atoms & lone
pairs present (how many H bonds can 1 molecule form?) H2O –
2, HF/NH3 – 1 only | greater extent of bonding = stronger
o Further applications of Hydrogen bonding:
 Intramolecular H-bonding
 Dimerisation of Carboxylic acids in non-polar solvent
 Ice & Water
 Simple molecular covalent lattices & physical properties

o Physical properties depend on the strength of intermolecular forces

o Generally, there is a low melting/boiling point as weak intermolecular forces
do not require much energy to overcome
 o Unable to conduct electricity on their own; but in water some can form ions
that act as mobile charge carriers: HCl (g) + H2O (l) -> H3O+(aq) + Cl- (g)
 Giant covalent/giant molecular lattices
o Diamond & Graphite are allotropes of carbon: different arrangements of C
atoms

o Diamond
 Each sp3 hybridised C atom is bonded to 4 other C atoms
 High melting & boiling point because of strong covalent bonds
between atoms that require large amount of energy to break
 Hard, strong & not malleable because of strong covalent bonds
 Unable to conduct electricity; no mobile charge carriers
o Graphite
 Each sp2 hybridised C atom is bonded to 3 other C atoms
 Each C atom contains unhybridised 2p orbital to form π bonding
system (basically benzene but in a chain) with a sea of delocalised
electrons
 Strong covalent bonds within each carbon layer
 (significant) id-id forces between layers (due to large surface area)
 High melting & boiling point because of strong covalent bonds
between atoms that require large amount of energy to break
 Good conductor of electricity as delocalised sea of electrons are free to
move within each layer -> by extension, electrons cannot cross
between layers -> graphite does not conduct electricity placed
perpendicularly to the layers
 Soft & slippery as the layers can slide over one another as the id-id
forces between them are weak
 Application of Chem Bonding: Solubility
 o A solute is soluble in a solvent if: the energy released from (solute-solvent
interactions, bond forming) is greater than or comparable to the energy needed
to overcome (solute-solute interactions) and (solvent-solvent interactions)
[bond breaking]
o must state the which species the interactions are between
o Hence, factors explaining solubility:
 type of interactions holding solute particles together,
 type of interactions holding solvent particles together,
 type of interaction that can occur between the solute and the solvent
particles,
 compare the strength of the new interactions (solute-solvent) with the
existing interactions (solute-solute and solvent-solvent)

Type of bonding How to identify?

Ion – dipole Cat/Anion and partial negative/positive charge on another
polar molecule

Hydrogen Bond H bonded to N/O/F [the lone pair can just come from N/O/F]
Pd – Pd Two polar molecules that don’t have hydrogen bonding
Pd - Id Polar – non-polar molecule
Id - Id Occurs in all molecules
Only type of bonding in non-polar molecules
 Note the strength of ion-dipole interactions depends on the charge
density of the ion, hence some salts e.g. AgCl are insoluble in water
o This however is an oversimplification:
 For the purposes of chem bonding, if something is soluble it can be
said to be an exothermic process
 However, that (obviously) isn’t true: Ammonium salts dissolve
endothermically; even NaCl’s dissolution is endothemic
 That is when entropy will have to come in to account for solubility by
ΔG = ΔH – TΔS
 Entropy change is not necessarily positive with 2 soluble compounds
(see Energetics)
 Solubility VS Miscibility
o Soluble implies that there is a saturation point where the solute can no longer
be dissolved in water (e.g. NaCl in water)
 at the saturation point, there may no longer be sufficient energy release
from the (now not present) solvent-solvent interactions
 o Miscible implies that there is no saturation point, you can add any volume of
solute & solvent and a homogenous mixture will be obtained (e.g. Ethanol &
Water)
 This is because the solute-solvent interaction is very similar to the
solute-solute/solute-solvent interaction
o Soluble/Insoluble generally refers to a solid – liquid combination
o Miscible/Immiscible generally refers to liquid – liquid
 Application of Chem Bonding: Physical Periodicity
o Melting point from Na to Ar

 Na, Mg, Al – giant metallic lattice of metal cations & sea of

delocalised electrons with strong electrostatic forces of attractions
between them
 Na to Al, number of valence electrons & cation charge density
increases as more energy is required to overcome the
 Stronger electrostatic forces of attraction between metallic
cation and sea of delocalised electrons
 [FYI] Mg and Al have similar melting points because packing
density or something; not important
 Si – giant covalent structure consisting of sp3 hybridised Si bonded to 4
other Si atoms
 strong Si – Si covalent bonds that require large amounts of
energy to break
 P4 , S8 , Cl2 – simple molecular structures with weak id-id
intermolecular forces
 Number of electrons determines strength of id-id forces
 Which means S8 has a higher melting point than P4
 Ar just exists as Ar atoms, same id-id story
o Electrical Conductivity from Na to Ar

 Na, Mg and Al have blah blah blah

 good electrical conductors because the delocalised electrons are
able to act as mobile charge carriers
 From Na to Al, the number of valence electrons and hence
number of charge carriers contributed per atom increases.
Therefore, electrical conductivity increases.
 Si – Ar: (state structure & bonding), all no mobile charge carriers
 However, Si is a metalloid (and semiconductor), hence its electrical
conductivity is non-zero
Chapter 3 – The Gaseous State
 Avogadro’s Law: Equal volumes of all gases, under the same temperature, contain the
same number of particles (atoms/molecules)
o 1 mole has 6x1023 particles, represented by η (NOT ηmol!!!)
 Relative Molecular Mass (Mr) is quite similar to relative atomic mass (Ar) in terms of
definition
o Average mass of 1 molecule of a substance relative to 1/12th the mass of a
carbon-12 atom
 Pressure is defined by force over area (P = F/A). the SI unit of pressure is pascal Pa
o BE VERY CAREFUL OF YOUR UNITS & WHAT IS PROVIDED IN THE
QUESTION!!! (they’re provided in the data booklet)
o Note “standard temperature and pressure” for this topic for some funny reason
is different from the rest of chem :(
 S.t.p for this topic is 293K and 1 bar
 S.t.p is 298K and 1 bar for EVERYTHING ELSE
mass
 The one thing you need to know: PV = ηRT, where η=
Mr
o Pressure is given in Pa, temperature in Kelvin, volume in m3
o TCelsius = TKelvin + 273
o Take note certain weird and funny questions may ask you to re-express R in
terms of the two molar gas constants provided in the question:
 Manipulating PV = ηRT:
o (ratio of variables) = constant
 For this type, as long as your units before and after are the same (eg all
volume in dm3), you can do the math, don’t worry too hard about SI
units
o Linear Law
 Follow Y = mX + C and you can plot graphs accordingly
 At a certain point, which value should be higher? (eg constant T, diff
number of moles. For a fixed value of V, P with more gas should be
higher)
 Dalton’s law of partial pressure
o In a mixture of non-reacting gases, each gas occupies the volume V of a
container and exerts its own partial pressure P on the walls of the container
o The total pressure is the sum of the individual pressures
η η
o P individual gas = Ptotal , where is known as the mole fraction
ηtotal η total
 Assumptions about an ideal gas
o Gas particles have negligible volume relative to the volume of the container
o There are no intermolecular forces of attraction between gas particles
o Collisions between gas particles and the walls of the container are perfectly
elastic (no loss of kinetic energy)
 A real gas will behave more “ideally” (follow PV = nRT) when …
o The pressure is low (volume of molecule negligible)
o The temperature is high (intermolecular force negligible)
 A real gas deviates from “ideal-ness” at…
o High pressure (low volume, particles close together, non-negligible volume) -
> gas molecules take up more volume than is predicted (at times the ideal PV
value may not even be possible because it’s smaller than the volume of gas
molecules) -> PV value is higher than ideal
o Low temperature (intermolecular forces are now more significant) -> gas
molecules closer together, PV value will be lower than ideal
 Representing deviation using graphs:
o Ideal gas has a line that is straight, non ideal will be below, then shoot above

o The greater the distance between the two lines, the greater the deviation from
ideal gas
 Explain the deviation using intermolecular forces/molecule size
 Larger molecule deviates more
 Stronger intermolecular forces deviates more
Chapter 4 – Redox and Stoichiometry
 Quick revision & summary:
o Relative (something) mass is the average mass of (something) relative to
1/12th the mass of a carbon-12 atom
o Exception for this is for relative isotopic mass, where the word “average” is
not needed
 Empirical formula is the simplest formula of a compound: it’s the RATIO of elements
o Table for calculating empirical formula based on their %masses:

Element
Mass in 100g of sample
Ar
η
Divide by smallest
number of moles
Ratio
 Molecular formula shows the ACTUAL NUMBER of atoms
o To get molecular formula using empirical, take the Mr and divide it by the
“Mr” of the empirical formula
o e.g. 176 = (C2H4O)n , therefore n = 176/44 = 4
 Balanced equations & mole ratio:
o (obviously) matter must be conserved -> in other words, for any reaction, the
elements in both the reactants and products must be the same
o USEFUL TIP FOR BALANCING CHEMICAL EQUATIONS WITH IONS:
Your charge has to stay the same throughout; balancing charge may give
you a little push in the right direction :)
o The coefficient of each reagent in a balanced equation will give you the mole
ratio (literally ratio of amount of substance that will react) – this serves as the
foundation for everything else
o FOR GASES ONLY: their volume ratio will give you the mole ratio as well
o FOR GASES ONLY: you can look at the molar volume for gases in the data
booklet at both s.t.p and r.t.p (this s.t.p is the gaseous state one)
 Limiting reagents & excess:
o X mol of (stuff) requires Y mol of (stuff) for complete reaction, but more/less
moles of Y is present as (compare values), therefore Y is in excess/the limiting
reagent.
actual amount of product
 yield of a reaction = ( 100% )
theoretical yield ( based on mole ratio )
 Redox Reactions!
o A process that involves REDuction and Oxidation simultaneously
 OIL RIG: Oxidation = gain e- ; Reduction = lose e-
 Oxidation = increase in oxidation state
  Reduction = decrease in oxidation state
 The number of electrons gained by the oxidising agent is equal to the
number of electrons lost by the reducing agent
 A reducing agent (RA) reduces something else by giving it
electrons, i.e. itself will lose electrons and be oxidised
 An oxidising agent (OA) oxidises something else by taking
away that thing’s electrons, i.e. itself gains those electrons and
is reduced
 Oxidation states
o The correct way to assign oxidation states
 (if compound is covalent) Draw out the Lewis structure
 Assuming each covalent bond is perfectly ionic, give the electrons in
each covalent bond to the more electronegative atom
 E.g C-Cl becomes C+ Cl-
 In monoatomic ions, the charge is the oxidation state
o General rules for assigning electronegativity:
 Elements have an oxidation number of zero
 In monoatomic ions, oxidation number = charge
 In polyatomic ions, sum of oxidation numbers = charge
 In neutral compounds, sum of oxidation numbers = 0
 Some general reference numbers to take note of for EN calculation:

Element Oxidation State

Hydrogen H +1 (except NaH, O.S. -1)
Oxygen -2 (except H2O2, O.S. -1)

o Solving half-equations: EOHC (Esther’s Open House Committee)

 E: balance elements
 O: balance oxygen using H2O
 H: balance hydrogens using H+, if reaction conditions are basic, add
OH- to both sides
 C: balance charge using e-
o Solving half equations using oxidation state:
 Find change in oxidation state (e,g I2 -> 2IO3-, I goes from from 0 to
+5)
 Add electrons to the side with higher oxidation state to balance out the
total oxidation (I2 -> 2IO3 + 10e-)
 Balance charge using H+ or OH- depending if solution is acidic/basic
 Balance out the equation with oxygen using H2O
 Check if hydrogens are balanced (they should be)
o Obtaining a full redox reaction from half equations:
 Make the number of electrons the same for both half equations using
their lowest common multiple (and then use mole ratio to change the
coefficients of the rest of the reactants)
 o Directly using the oxidation state to get a full reaction:
DISCLAIMER: Your grasp of oxidation state must be VERY GOOD for this
to work
 Let’s take the oxidation of alcohols by MnO4-:
 CH3CH2OH + MnO4- -> Mn2+ + CH3COOH
 Total increase in oxidation state must equal to total decrease in
oxidation state (use LCM)
 Oxidation state of the CARBONYL CARBON goes from -1 to +3 (+4
OS) | oxidation state of Mn changes from +7 to +2 (-5 OS), LCM is 5 x
4 = 20
5CH3CH2OH + 4MnO4- -> 4Mn2+ + 5CH3COOH
 Balance the charge using H+/OH-, then use H2O to balance the oxygen.
Finally, check if hydrogen is OK!
 Eventually after that you’ll get:
12H+ + 5CH3CH2OH + 4MnO4- -> 4Mn2+ + 5CH3COOH + 11H2O
 The rest of pure stoichiometry is really just math: BE. VERY. CAREFUL.
o [S2O82-] refers to concentration of S2O82-
o When doing calculations, just double check your workings are correct by
checking if the units all add up:
 E.g. Amount of a gas (mol) = Volume of gas(dm3)/Molar volume
(dm3mol-1)
o However, as it is with math (and physics), you need to know WHAT your
units are representing :)
 Is this an analyte taken from a standard solution? If so, how much of
the actual solution is being used?
 Is the solution diluted from its original form? (e.g equal volume of [A]
and [B] were reacted together = the concentration is halved from initial
value!!!)
 When using amount = concentration x volume, what is your
concentration referring to? [S2O82-] in the 250cm3 volumetric flask? or
[S2O82-] of the undiluted reagent? then multiply by corresponding
volume
Chapter 22 – Periodicity
 Period 3 trends
o Phosphorous P exists as 2 forms: White (P4) and Red (P4)n
o Red phosphorous is a lot more stable as has a polymer structure, and thus less
bond angle strain

o Quite a bit of overlap from Ch 1 & 2

 For m.p graph, Al & Mg are similar (because packing efficiency)
 P4 is lower than S8 because of the id-id forces & electron cloud story,
P8 will still be higher than S8
 For the conductivity, Si CANNOT!!! be zero because it is a
semiconductor
 the m.p of oxides and chlorides will be your LE, giant covalent, simple
covalent story
o Variation of oxidation number
 The maximum oxidation state +x = number of valence electrons x
  P, S and Cl can hold a wider range of O.S because it can expand its
octet using d orbital
o Oxides
 Structure and bonding – remember that SiO2 is giant covalent like
diamond :)
 Melting point of Na2O, MgO and Al2O3
q−¿
 Na2O vs MgO is the usual Zeff + |LE|∝ |q + ¿ | story
r +¿+ r ¿ ¿
−¿

 MgO however, has a higher m.p than Al2O3 :(

o Al3+ high charge density, can polarise O2-, Al2O3 has
more covalent character and thus will deviate from
expected LE trend
 Drawing SiO2:
 Its structure doesn’t exactly look like diamond
 TL:DR Si can form 4 bonds like C, O cannot.
 The yellow bits are O atoms that can no longer form bonds to
extend the giant covalent lattice
 The blue bits can still extent, albeit only downwards

 P4O10
 Drawing looks like this:
 BTW while 1 “PO4” thing is polar
as dipole moment of C=O is not the
same as C-O, P4O10 isn’t polar as the
whole molecule is “tetrahedral” =>
the 4 C=Os are arranged
“tetrahedrally”
 Chlorides
o Structure, Bonding, Melting Point
 Same as Ch 1 & 2, NaCl/MgCl2 are ionic, SiCl4/PCl5 are simple
covalent (just note PCl5 is a solid at r.t.p, PCl3 is a liquid)
  PCl5 can ionise into PCl4+ and PCl6- -> strong ionic interactions
increase the melting point so it’s a solid
 The exception: AlCl3
 In vapour phase, AlCl3 is simple covalent, forming an equilibrium with
gaseous Al2Cl6 dimers
 AlCl3 is covalent because Al3+ has high charge density -> polarising
power high + Cl- is large -> low charge density -> very polarisable
 Time for reactions :(
o Very very fast and quick summary:
o Metal (ionic) oxides are basic | Na, Mg
o non-metal (covalent) oxides are acidic | Si, P, S, Cl
o Al2O3 has both ionic & covalent character due to the high polarising power of
the Al3+ ion, this can behave as either acid or base (amphoteric)
o Amphoteric oxides: ZAP – Zinc, Al, Pb (lead)
o These are not redox reactions; hence the oxidation state of the period 3
element will not change :)
o Your charge has to stay the same throughout; helpful in determining the
amount of H+ / OH- needed :))
 Reactions of Period 3 oxides
o Reactions with water
 metal oxides contain the O2- ion, which is a strong strong base and
reacts with H2O to give OH- (i.e. metal hydroxide)
 Na2O + H2O -> 2NaOH | pH = 13 | vigorous & exothermic
 MgO + H2O -> Mg(OH)2 | pH = 9 | slow reaction; Mg(OH)2 sparingly
soluble
 Al2O3 is insoluble in water (very negative LE) i.e. pH = 7
 SiO2 has no reaction with water (strong Si-O covalent bond) i.e. pH = 7
 acidic oxides react with water to form the respective acid:
 P4O10 + 6H2O -> 4H3PO4 | pH = 2 | violent
 SO3 + H2O -> H2SO4 | pH = 1 | violent and exothermic
 [FYI] P4O6 + H2O -> H3PO3 (a DIBASIC!!! acid)
 [FYI] SO2 + H2O -> H2SO3
o Reactions with acids (metal oxides)
 React the oxide with water, then H+ (neutralisation)
because remember an acid has to be aqueous; got water
 Gives you the metal cation & water:
 Na2O + 2H+ -> 2Na+ + H2O
 MgO + 2H+ -> Mg2+ + H2O
 Al2O3 + 6H+ -> 2Al3+ + 3H2O
o Reactions with NaOH (covalent oxides)
 Forms the anion of the acid/salt (for Al, it’s the aluminate)
 Al2O3 + 2OH- + 3H2O -> 2[Al(OH)4]-
 Al(OH)3 + OH- -> [Al(OH)4]-
 for BOTH of these, the base must be in EXCESS (remember your QA,
white Al(OH)3 ppt soluble in excess NaOH)
 SiO2 + 2OH- -> SiO32- + H2O
Only possible in hot, concentrated NaOH
 P4O10 + 12OH- -> 4PO43- + 6H2O
 (what I mean about conserved charge) you have 4P in P4O10 -> 4PO43-
formed > total charge is 12- -> 12OH- required
 SO3 + 2OH- -> SO42- + H2O
 Reactions of the metal chlorides (NaCl, MgCl2, AlCl3)
o charge density of cation is important
o Down the period, Z increases, shielding effect and number of quantum shells
remains relatively constant -> Zeff increases, ionic radius will decrease + the
charge of the cation increase
o i.e. charge density of cation increases from Na+ to Mg+ to Al3+
o Higher the charge density, higher the extent of hydrolysis:
o What’s hydrolysis?
o The hydrogen in H2O is already δ+, then you have a metal cation that polarises
the H2O electron cloud even more -> H becomes very very δ+, O-H bond
becomes weaker, allowing the H atom to become acidic in nature

o BTW the bonds in complex ion are ion-dipole interactions, for high charge
density cations like Mg2, Al3+ (and in TM chemistry) they can be considered
covalent bonds due to polarised electron clouds
o Just note (especially when compared to organic chem’s hydrolysis) this is a
rare case where hydrolysis = acid-base reaction
o Extent of this hydrolysis depends on the charge density (hence polarising
power) of the metal cation
o NaCl (s) -> Na+ (aq) + Cl- (aq)
 Low CD, hydrolysis does not occur
 pH = 7
o MgCl2 (s) + 6H2O (l) -> [Mg(H2O)6]2+ (aq) + 2Cl- (aq)
o [Mg(H2O)6]2+ (aq) + H2O (l) -> [Mg(H2O)6]2+ + H3O+ (aq)
  Mg2+ has moderate charge density -> slight hydrolysis occurs
 pH = 6.5
 Hence MgCl2 cannot react with CO32- to form CO2 gas
o [Limited water] AlCl3 (s) + 3H2O (l) -> Al(OH)3 (s) + 3HCl (g)
 HCl given off as steamy white fumes , Al(OH)3 is a white solid
o [Excess water] AlCl3 (s) + 6H2O (l) -> [Al(H2O)6]3+ (aq) + 3Cl- (aq)
o [Al(H2O)6]3+ + H2O (l) -> [Al(H2O)5(OH)]2+ + H3O+ (aq)
 Al3+ has a very high charge density -> O-H bond in [Al(H2O)6]3+ are
sufficiently polarised & weakened to donate protons
 Further extent of hydrolysis in the Al complex than Mg
 (distinctly) acidic solution, pH = 3
 Hence AlCl3 can react with CO32- (a base) to form CO2
 2[Al(H2O)6]3+ + 3CO32- -> 3CO2 + 3H2O + [Al(H2O)3(OH)3]
o This also means AlCl3 can react with NaOH to deprotonate the [Al(H2O)6]3+
complex; this occurs 3 times
 Overall: [Al(H2O)6]3+ + 3OH- -> [Al(H2O)3(OH)3] + 3H2O
 [Al(H2O)3(OH)3] is basically Al(OH)3 ; white ppt
 IN EXCESS NaOH: Al(OH)3 + OH- -> [Al(OH)4]- complex
 Reactions of the covalent chlorides (SiCl4 , PCl5)
o SiCl4 is a colourless fuming liquid; PCl5 a solid (because of the ion thingy)
o Complete hydrolysis occurs to form HCl -> solutions are strongly acidic | pH
= 1 if water is in excess; HCl (g) -> HCl (aq)
o Violent reaction with water to produce white HCl fumes
o works even with moist air! -> chlorides must be kept in airtight containers
o SiCl4 (l) + 4H2O (l) -> SiO2•2H2O (s) + 4HCl(g/aq)
o PCl5 (s) + 4H2O (l) -> H3PO4 (aq) + 5HCl (g/aq)
o [if water added dropwise]
PCl5 (s) + H2O (l) -> POCl3 (l) + 2HCl (g)
 Some other fun facts relating to this section
o [Fe(H2O)6] is most acidic out of the M3+ cations Al3+, Fe3+, Cr3+
o Extra elaboration on why MgCl2 doesn’t react with CO32-:
 pKa Mg2+ = 11.4, pKa H2CO3 = 6.35 (1st) , 10.3 (2nd)
 HCO3- is a stronger acid that Mg2+ => CO32- will not react with Mg2+ to
give the stronger acid-base pair
o (H3-ish) Mechanism of hydrolysis & NCl3 story
 PCl3 + 3H2O -> H3PO3 (the dibasic acid!!) + 3HCl
 PCl5 hydrolyses via a “SN2-elimination” mechanism of sorts, with the
LP of electrons on O (in either water of a say, alcohol) attacking the
electron deficient central P atom before the Cl- is kicked out
 which is why in both POCl3 and PO43-, you’ll have a P=O bond; it
comes from the formation of a P=O bond kicking out Cl
 N is a period 2 element; and doesn’t have energetically accessible d-
orbitals (unlike Period 3 P) to undergo “SN2-elimination” like
 PCl5/PCl3 does; in fact, N central atom in NCl3 is a nucleophile with its
lone pair!
 NCl3 actually goes through a different mode of hydrolysis, where Cl is
the electrophile (rmb EN N > EN Cl) and -NCl2 acts as the LG
 NCl3 + H2O -> NHCl2 + HOCl
o CCl4 vs SiCl4
 Because Si is a larger atom than C, there is more effective orbital
overlap & less steric hindrance by the Cl groups
 C also has no energetically accessible d-orbitals, and unlike NCl 3, it
will be the electrophile (not the Cl)
 Group 2 Metals
o Link to E-Chem: Eº values become more negative because … -> atomic radius
increase -> electrons are lost (oxidised) more readily -> reducing power
increases down the group
 Group 2 Carbonates:
o Unstable towards heat | MCO3 -> MO + CO2
o Become more thermally stable down the group -> decomposition
temperature higher
o Diagram of decomposition

o So why the variance?

 Group 2 cations have a high charge density
 The stability of carbonates is affected by this C.D
 Cationic radius increases down the group b/c more quantum
shells => C.D increases down the group
 Higher CD, polarising power decreases -> less able to distort
the electron cloud of CO32- -> C – O bond is weakened to a
smaller extent
 Thus energy required to decompose the carbonate is higher
(thermal stability increase)
 Extension to group 1 carbonates
 Group 1 carbonates resistant to decomposition except Li2CO3 -
> b/c Li+ very small, high CD
o This logic also applies to other oxyanions BTW:
 Group 17: Halogens
o General Properties
 remember again, the difference between INTER and INTRA molecular
bonding!!! (eg iodine)
 F2/Cl2 are gases, Br2 is a liquid, I2 is a solid (about INTERmolecular id-
id forces)
 Useful thing to take note for halogens is their colour in hexane/organic
solvent (in Data Booklet) -> not that easy to tell apart
yellow/orange/pale brown in the lab especially without a reference
 Halogens are oxidising agents as they tend to accept an electron to
form the halide anion
 As for strength, start with Eº values first, unless you need to explain the
strength, then talk about the ability to accept electrons (atomic radius)
o Redox reactions of halogens
 Halogen Displacement reactions (Cl2 + 2KI -> 2KCl + I2)
 The more reactive halogen gas displaces the less reactive one
 “Reactive” in this case means the stronger OA (higher up the
Group) ; more likely to gain electrons and reduce
 Also implying that halide ions become stronger RAs down the
group (more willing to lose the extra electron)
 Reactions with thiosulfate
 Equations will be provided in the exam
 What is important to note is that the weaker the O.A., the
smaller the change in oxidation state of the sulfur atom (I2 vs
Cl2/Br2)
 o Thermal stability
 This is about INTRAmolecular bonding: the strength of the H – X
bond (bond length; extent of orbital overlap)
 MUST KNOW THE DECOMPOSITION BEHAVIOUR:

 Useful thing to note about Periodicity:

Chapter 23 – Transition Elements
 Definitions
o (at A levels) Transition elements are d-block elements that form 1 or more
stable ions with partially filled d-subshell
 Hence by this, Sc and Zn are not TMs as they only form 1 ion: Sc3+,
Zn2+ respectively (they are by IUPAC’s definition FYI)
o A complex is a molecule/atom formed by a central metal atom/ion surrounded
by 1 or more ligands.
o A ligand is an ion/molecule with 1 or more lone pairs of electrons to be
donated into the vacant d orbitals of a transition metal atom/ion.
 Recap of concepts
o Still quite a lot about Atomic Structure
o please please please remember that when writing the electronic configuration
of TMs, the 4s electrons are both filled and removed FIRST!!!
o The 3d4 4s2/3d9 4s2 (wrong) -> 3d5 4s1/3d10 4s1 (correct) rule: having a
half/fully filled set of d-orbitals
o for A levels, d-electrons are considered “core electrons”
 your valence shell is the 4s shell
 but in TM you fill the 3d subshell (below 4s)
 used to explain the relative invariance of IE in transition elements
 shielding effect increase, Z increase, Zeff relatively constant and
number of quantum shells stays constant
 BTW from Mn2+ d5 s2 -> Fe2+ d6 s2, there is an decrease in IE due to the
presence of interelectronic repulsion (Fe is lower than expected)
 Summary of Properties of Transition elements:
o Variable Oxidation States
o Catalytic Properties (both homo & heterogenous catalysis)
o Formation of Complexes
o Coloured ions
 Variable Oxidation States

o high oxidation state TMs are not found as free ions but in polyatomic ions (e.g
MnO4-)
o (as with quite a bit of this topic) you can explain things with “energy level of
3d subshell is similar to that of 4s”
 o i.e. when 4s e- are removed, 3d e- can be removed without too much extra
energy
o The number of possible O.S. increases from Ti to Mn then decreases to Cu
 Before Mn (3d1 -> 3d5), there are more available d-electrons to lose,
therefore max oxidation state is highest
 After Mn (3d5 4s2), max O.S. decreases from +7 because pairing of d-
electrons occurs, so fewer d-electrons can be lost after the 4s ones
 e.g. Ni (3d8 4s2) only has 2 unpaired d-electrons, hence its max O.S. is
2 + 2 = +4
 Catalytic properties
o TMs can exist as catalysts due to presence of energetically-accessible d-
orbitals & variable oxidation states
o In heterogenous catalysis, the substrates adsorb using the partially-filled d-
orbitals of the TM
o Mechanism of a TM homogenous catalyst
 You WILL need to talk about the Eºcell of each step, sucky as it is :(
 Generally speaking, if Eº(oxidised) < Eº(catalyst) < Eº (reduced), the
catalyst will work
 because the catalyst will react with both species separately; you can
balance redox reactions on the spot using data booklet if you don’t
want to memorise
 just know what is getting oxidised & reduced
 The I- - S2O82- reaction is actually energetically feasible but not
kinetically feasible (the negative charge repelling thingy)
Eº (I2 | I-) = + 0.54V, Eº (S2O82- | SO42-) = + 2.01V
2I- + S2O82- -> I2 + 2SO42- , Eºcell = +2.01 – 0.54 = +1.47 > 0!
 Eº (Fe3+ | Fe2+) = +0.77V ; + 0.54 < +0.77 < +2.01
 Fe3+ is a suitable catalyst because both steps will involve collisions
between oppositely charged ions & it has presence of vacant d orbitals
& variable oxidation states
 2Fe3+ + 2I- -> 2Fe2+ + I2 | Eºcell = 0.77 – 0.54 = 0.23
 2Fe2+ + S2O82- -> 2Fe3+ + 2SO42- | Eºcell = 2.01 – 0.77 = 1.24
 They can also test other stuff like Fe2+ & H2O2:
 Eº (H2O2 | H2O) = + 1.77 , Eº (O2 | H2O2) = + 0.68
 0.68 < 0.77 < 1.77 so yes this works :)
o Other than that go revise kinetics; it’s the same story as before (e.g. mode of
action of a catalyst)
o Evidence of catalysis:
 increased (you have to compare!) rate of reaction
 e.g. Fe2+ catalysed decomposition of H2O2 into O2 + H2O:
vigorous effervescence
 Colour changes
 must go BACK to the original colour
  All about the idea of regeneration
 prescence of an intermediate
 if mechanism given, can cite mechanism and explain (if possible) how
the catalyst will lower Ea
 catalysts are only needed in small amount
 watch out for stuff like “few drops of”
 Transition Metal Complexes
o When you write CuSO4 (aq), Cu2+ (aq)
isn’t just some random free ion, but
has ion-dipole interactions! (see left)
o The difference between ion-dipole
interaction & ligand bonds will be the
charge density of the ion involved
o TM cations have high charge density
hence the electron cloud of the ligand
is polarised, leading to greater
covalent (dative) character
o TM cations have energetically-
accessible & vacant 3d-orbitals (and 4s + 4p too) to act as Lewis acids &
accommodate this lone pair of electrons
o In fact, it’s another spectrum:
 Ion-dipole -> Hydrogen bonding -> dative bonding
o Cu exists as an “aqua-complex” (aqua meaning water) [Cu(H2O)6]2+
2+

 Complexes exist as an entire polyatomic ion; and can thus form salts
such as [Cu(H2O)6]SO4
o Each H2O bonds datively to the cation using it’s lone pair of electrons, and is a
Lewis base

 Ligands
o Number of bonds formed with a central ion
  Monodentate – 1 bond per ligand
 Bidentate – 2 bonds per ligand
 Polydentate – multiple bonds per ligand
o Chelation
 Polydentate ligands are able to hold a metal ion like a “claw”
 Hence, complex ion is more stable (more electrostatic forces of
attraction needed to remove that ligand)
o Examples of ligands

o [FYI] Why will the EDTA complex be stable/formed so readily?

 Entropy driven!
 [Co(NH3)6]2+ + [EDTA]4- -> [CoEDTA]2+ + 6NH3
 ΔS is very positive (2 moles of ion gives 7 moles of ions as products)
 Link back to ΔG = ΔH – TΔS
 “TΔS” > 0 leads to ΔG being < 0
 ΔG = -RTlnK ; K will also be positive, PoE to the right
 Geometry of complexes:
o DO NOT!!! SOLELY USE VSEPR!!!
o Co-ordination number = number of dative bonds around central ion
o Most common values are 4 and 6
o For Ag+ and Cu+, co-ordination number is 2

o Application of geometry: Chirality

 Complex ions can be chiral!
 The rest of the story is just normal isomerism
 Acidity of aqua complexes (very similar to Periodicity)
o Just like Al3+, TM metal cations have high charge density
o blah blah blah same hydrolysis story
o For especially high oxidation states (>3+), the extent of proton loss & is so
great that oxoanions are formed
 [Cr(H2O)6]6+ doesn’t exist, but as CrO42- and Cr2O72-
 [Cr(H2O)6]3+ + 3OH- -> [Cr(H2O)3(OH)3] + 3H2O
 OR: Cr3+ + 3OH- -> Cr(OH)3 (grey-green ppt)
 [Cr(H2O)3(OH)3] + 3OH- -> [Cr(OH)6]3- (dark green solution)
 2CrO4- + 2H+ ⇌ Cr2O72- + H2O (O.S. of Cr DOESN’T CHANGE)
  Ligand Exchange Reactions
o Ligands can replace each other in SN2 fashion
o When talking about Kc expressions for ligand exchange reactions: [H2O] is a
constant -> you DON’T!! use it for LCP & PoE
EXAMPLE: Dilution of CoCl42- with H2O reforms [Co(H2O)]2+
o CoCl42- + 6H2O ⇌ [Co(H2O)]2+ + 4Cl-
o Addition of water reduces the concentration of all ionic species by the same
factor
2+ - 4
[[Co ( H2 O)6 ] ] [ Cl ]
o Qc = 2-
[ (Co Cl 4 ) ]
o Since there are more terms on the RHS of the equilibria compared to the LHS,
numerator decreases more and Qc < Kc
o For Qc to equal Kc again, the PoE will shift left to increase [[Co(H2O)]2+] and
[Cl-] as well as decrease [CoCl42-] to increase the numerical value of Qc
 Table of aqueous complex ions to know

Cation/Ligand H2O NH3 Cl- OH-

Cu2+ 6 4 (dark blue) 4 (yellow) -
3+
Al 6 4
3+
Cr 6
3+
Fe 6
2+
Zn “6” 4 4
+
Ag 2 2 - -
- 3+
o SCN only replaces 1 H2O in [Fe(H2O)6]
 Colour of TM cations/complexes
o The Colour Wheel
 Important to know that the observed colour of the thing is on the
OPPOSITE SIDE from what wavelength of light is absorbed
o Crystal Field Theory
 In a free TM cation, all 5 d-orbitals are degenerate (same energy)
 (just like physics) the LP on a ligand is treated as a point negative
charge that are attracted to the cation and repelled by d-electrons
 The presence of ligands will create an octahedral ligand field that will
increase the average energy of the d-orbitals
 However, the ligands approach along the x/y/z axes
 Hence, the extent of repulsion will be different are 3 d- orbitals are in
between the principal axes, while 2 d-orbitals lie on the axes
 The d-orbitals lying on axes will experience stronger repulsion -> no
longer of the same energy, degeneracy lost
  The final ΔE between the d-orbital energy levels corresponds to the
energy of photons of wavelength in the visible spectrum (400 –
hc
700nm) by the formula ΔE =
λ
 When this photon is absorbed, an electron from the lower energy level
is excited to the higher energy level, leaving “missing light” from
incident white (ROYGBIV) light
 i love nuclear physics!!!! yay!!!
o Factors affecting complex colour
 literally just “ΔE changes”
 Oxidation state of metal
 Nature of ligand
o Story to vomit in exam regarding complex colour:
 Ni2+ has partially filled d-orbitals (important because fully filled d-
orbitals will result in no colour observed e.g. Cu+ in cream CuI)
 In presence of ligands, degenerate d-orbitals split into 2 distinct energy
levels with energy gap ΔE
 When light shines on the solution, the electrons from the lower energy
level will absorb light at a specific wavelength corresponding to ΔE
and is promoted to a vacant orbital at a higher energy level
 The wavelength of light absorbed corresponds to the wavelengths of
visible light
 The colour seen is the complementary colour of the colour of visible
light absorbed
o When discussing colour change:
 The complementary colours are seen, so the colour of each complex
will be different
 When (whatever e.g. ligands change from H2O to NH3), the magnitude
of energy gap ΔE also changes, so the solution changes colour