Crystalline solids: made up of essentially regular

arrangement
Three common unit cell
Density of crystal (D) g/cm3

Closest packing model (crystal):

Atoms/ions/molecules packed so as to most
efficiently use the space available
Interstices: space b/w the spheres
Interstitial sites

Amorphous solids: disordered

-Simple/ primitive cubic (sc); 52%
-Body-centred cubic (bcc); 68%
-Face-centred cubic (fcc); 74%
F.W. x Z/NA x V
F.W. (g) mass of a mole of the formula
NA : 6.022 x 1023
V : a3 (for cubic unit cell)
Z: 1 for Po, 2 for bcc, 4 for fcc
Hexagonal close packed: hcp array
aba arrangement
cubic close packed: ccp array
abc arrangement
each atoms coordination no: 12
Tetrahedral (b/w 3 closed packed spheres)
and octahedral (b/w 2 sets of 3 speheres)

METALLIC BONDING
Delocalized valence electrons are responsible for high thermal and conductivities of metal
Band theory
N atomic orbitals are combined to form N
Band: continuum of energy levels
molecular orbitals, half of which are bonding
molecular orbitals, the other half,
antibonding molecular orbitals
The larger N the more molecular orbitals that
are formed and the closer in energy the
bonding and antibonding become
Metals are characterized by having a band
Difference b/w semiconductors, metals and
structure in which the highest occupied band is
insulators depend on:
partially filled
Band structure
Valence bands are full/partially filled
Magnitude of energy gap b/w full and empty
bands
Insulators: band gap is very large; very few
n-type semiconductors: more valence electrons than
electrons have sufficient thermal energy to be
silicon
promoted to the empty band above
p-type semiconductor: less valence electron than
Semiconductors: band gap not as large; a few
silicon
electrons have sufficient thermal energy to be
promoted; hence conductivity increases with
increasing temperature.
Electrons that are promoted into conduction band
are regarded as negative charge carriers. The
vacant electron levels left behind are called
positive holes

TRENDS IN MAIN GROUP CHEMISTRY

Group 1A

Weak metallic bonding

Alkali metal
Very open structure
Low mp; Regular decrease of mp down the
group
Very soft
Group 2A
Alkaline earth metal
Much harder, more dense
Stronger bond due to 2 valence electrons
General but irregular decrease in mp down
the group
Several group trends in the periodic table
Zeff increases slightly down the group
First IE decrease going down the group
Atomic size increases down the group
Electronegativity decreases down the group
1A metals:
2A metals:
react vigorously with water (v. exothermic) hence -Ca, Sr, Ba behave just as the 1A group
must be stored under oil
-Be does not react with water; Mg only reacts with
+
2M (s) + 2 H2O (l) -> 2M (aq) + 2 OH (aq) + H2 (g) steam
-Mg is protected from most chemicals by a thin
coating of water insoluble MgO. Be only reacts with
non-metals at high temp.
Lithium is the only alkali metal that reacts with N2 Be2+ form compounds that are essentially covalent
6 Li(s) + N2 (g) -> 2 Li3N (s)
due to its small size
In 3A, B is a metalloid, forms covalent molecular
Despite both being in 4A, C and Si have different
compounds (eg. BX3)
properties:
C is able to form stronger pi-bonds
C is more electronegative
Si is larger
Si has available empty d-orbitals
These 4 factors can be used to explain the difference
in properties b/w N and P in 5A; O and S in 6A
Some periodic trends going from left to right:
Zeff increases going across
First IE generally increases
Atomic size decreases
Electronegativity increases
Fluorine is a pale yellow gas
-high reactivity of F is primarily due to the weak F-F
Chlorine is a yellow-green gas
bond; F is a very strong oxidising agent
Bromine is a reddish-brown liquid
Iodine is a grayish-black solid that sublimes into
violet vapour at r.t.
Si is a metalloid; in period 3, from left to right the
elements become less metallic in properties.

White P: contains discrete tetrahedral P4,

v.reactive in air and hence must be stored under
water
Black and red P: network solids, much less
reactive.
-Black p- regular crystalline solid, 3-coordinate P
atoms) most stable form under normal conditions.
-Red p- amorphous, chains of P4. Heating white P
under anerobic conditions gives red P, black P can
be prepares by heating under white or red at high
pressure.
Li2O, Na2O, MgO are called basic
oxides/anhydrides
M2O (s) + H2O (l) -> 2M+ (aq) + 2OH- (aq)
CO does not dissociate in water whereas CO2 is an
acidic oxide
CO2 + H2O -> H2CO3 ( a weak and diprotic acid)

-S is found in the earths crust as S8, at r.t. exists in

rhombic sulfur form.
-At 113C, S melts to form a liquid that contains S8, in
cooling monoclinic sulfur (2nd allotrope) is formed.
-Further heating produces chains of Sn
-rapid cooling forms plastic sulfur Sn

Amphoteric oxides (can behave as base or aicd)

Eg. BeO and Al2O3
BeO + 2H+ -> Be2+ + H2O
BeO + H2O + 2OH- -> Be(OH)42-

TRANSITION METAL CHEMISTRY

The last electrons added for the transition metals are d or f electrons; these are inner electrons and do
not as readily participate in bonding as s or p electrons
1. Often more than one o.s.
Ionic compounds of transition metals
2. The cation is often a complex ion, formed
because the central is surrounded by
ligands (which behave as lewis base). The
bond is known as co-ordinate covalent
bonds. The resulting complexes are known
as co-ordination compound.
3. Often coloured
4. Often paramagnetic

First Row Transition Metal

Valence configuration:
Sc-4s2 3d1 Mn- 4s2 3d5
Ti-4s2 3d2 Fe- 4s2 3d6
V-4s2 3d3 Co- 4s2 3d7
Cr-4s1 3d5 Ni-4s2 3d8
Common o.s. :
Sc +3
Ti +2, +3, +4
V +2,+3,+4,+5
Cr +2,+3,+6

Cu-4s1 3d10
Zn- 4s2 3d10

Mn +2, +3, +4, +7

Fe +2, +3
Cu +1, +2
Co +2, +3
Zn +2
Ni +2

Ionization energies:
Generally increase going across the period .
I3 increases more rapidly than I1.

Co-ordination Compounds:
Coord no. Geometry
6
Octahedral
4
Tetrahedral or square planar
2
Linear
Pt2+ always forms square planar complex, Pd2+nearly
always and Ni2+sometimes.
Ligands:
Unindentate: single donor atom (one pair of e-)
Bidentate: two donor atoms (2 pairs of e-). If both
donor atoms are bound to the same metal ion, they
are called chelate.
Polydentate:3 or more donor atoms

Standard reduction potential:

Structural isomerism:
All of the first row transition metal except copper
1. Ionisation isomerism eg. CrSO4(NH3)5Br
can reduce H+ ion to hydrogen gas in 1M solutions
and . CrBr(NH3)5SO4
of strong acid.
2. Co-ordination eg. Cu(NH3)4PtCl4 and
Reducing abilities generally decrease across the
Pt(NH3)4CuCl4
period Sc>Ti>V>Mn>Cr>Zn>Fe>Co>Ni>Cu (Cr and
3. Linkage eg. CoCl(NO2)(NH3)4Cl and .
Zn do not follow this trend.
CoCl(ONO)(NH3)4Cl (different point of
attachment

Atomic radii:
Generally decrease across the period. There is a
significant increase in size from 1st to 2nd row but
not to the 3rd due to Lanthanide contraction

Stereoisomersm: same bonding sequence but

differ in spatial arrangement of the atoms
Geometrical Isomerism: cis-trans, facialmeredional
Optical isomerism:
-Non-superimposable mirror image isomers,
optically active because when plane polarized light
is passed through a solution containing one of them
the plane is rotated.
-Dextrorotatory: (+) clockwise
Levorotatory: (-) anti-clockwise
-absolute configuration
-diastereomers

Bonding in Transition metal complex:

-Valence bond theory
-octahedral, tetrahedral, square planar, linear
-VSEPR model can be used to explain the shape of
the complex ion and hybridization to explain the
bonding. Hence sp3d2, sp3, dsp2 and sp
hybridization of transition metal ion can be
invoked in octahedral, tetrahedral, square planar
and linear complexes.

Magnetic Properties of First Row Transition

Metal Complexes
1. Most of the transition metal elements are
paramagnetic. From magnetic
measurements, the number of unpaired
electrons can be deduced and often
information about its stereochemistry.
2. Each spinning movement of electron in a
closed path about the nucleus result in
magnetic moment, , the total of which is
the sum of the spin moment, s and an
orbital moment 1. The effects of the latter
tend to be quenched as a result of the
neighbouring atoms or ions.
3. s = no.of unpaired electrons
s = n(n+2)
n: no. of unpaired electrons, measured in
BM, 1BM= 9.274x10-24 JT-1.
Good agreement between calculated and
experimentally observed magnetic moments
is often found for complexes containing 1st
row transition metal ions.

Pauling Valence Bond Theory:

Magnetic properties depend on whether or not the
specific d orbitals were available after account had
been made for those used in hybridization.

d-electrons effect
The d-electrons are inner electrons and as such do
not as readily participate in bonding as electrons

Inner orbital complex: 3d orbitals of the

metal ion are invoked in hybridisation
Outer orbital complex: 4d orbitals of the
metal ion are invoked in hybridization
The colour and magnetism result from
changes in the energies of the the d orbitals
on the metal ion cause by metal-ligand
interaction.
Crystal Field Theory (CFT)
Focuses on the relative energies of the d orbitals in
transition metal complexes.

in s and p valence orbitals.

The d electrons do influence the coordination
number of the metal ion and changes in the energy
level of the d-electrons are responsible for such
properties as the colour and magnetism of the
complexes.

Strong field/low spin: happens when the

splitting of the 3d orbitals is large, whereby the d
electrons will pair in the lower t2g set ->
paramagnetic
- 0 < P, P: mean pairing energy of the d electrons.

Assumes that ligands can be approximated

by negative point charges and the metalligand-bonding is entirely ionic.
The splitting of the energies of 3d orbitals
explain the colour and magnetism of
complex ions of the 1st row transition metal
ions.
Centre of gravity rule: in a purely
electrostatic field the pattern of splitting is
such that the algebraic sum of all energy
shifts of all orbital is zero.

Weak field/high spin: arises when the splitting of

3d orbitals is relatively small, whereby the 3d
electrons occupy both the t2g and eg sets before
pairing can occur (Hunds rule) (yields max no. of
unpaired electrons) -> diamagnetic

Studies on many octahedral complexes containing 1st row transition metal ions have shown that ligands
can be arranged in order of their ability to produce splitting of the energies of the 3d orbitals.
Spectrochemical series: CO>CN->NO2-> en(ethylenediamene)>NH3>py>NCS->H2O>OH->F->Cl>SCN>Br>I (the order is from large 0 to small 0)
-the magnitude of 0 for a ligand increases as the charge on the metal ion increases
-the largest P is found for the d5 configuration and hence complexes containing a d5 metal ion eg. Mn2+
or Fe3+ are exceptionally stable in the high spin state.
-nearly all Co(III) complexes on the other hand have low spin configuration (except CoF63- )
-complexes containing divalent (valency of 2) 1st row metal ions are typically high spin
Tetrahedral Complexes
Colour of 1st row transition metal
d0 VO2+ yellow, Cr2O72- orange, CrO42- yellow, MnO4 None of the d orbitals point towards the
purple
point of charge ligands in a tetrahedral
d1 Ti(H2O)63+ purple, VO(H2O)52+ blue
complex.
The t2 set are closer to the negative poin tin d2 V(H2O)63+ blue-green
charge than the e set. Hence the t2 set occur d3 V(H2O)62+ violet, Cr(H2O)63+ violet
at higher energy.
d4 Cr(H2O)62+ sky blue

t is small hence invariably high spin,

d5 Mn(H2O)62+ pink, Fe(H2O)63+ colourless

t =4/90
d6 Fe(H2O)62+ light green
Favoured if the central atom is small or the d7 Co(H2O)62+ rose
ligands large for then the steric effects
d8 Ni(H2O)62+ emerald green
override the energy advantage of forming
d9 Cu(H2O)62+ blue
metal-ligands bonds.
A substance exhibits the complimentary colour of
the colour absorbed.

Manganate and CrO42- have no d electrons and owe

their colour to charge transfer absorptions. Here
absorption of light in the visible region results in
excitation of an electron from a ligand based
orbital to an empty d orbital on the metal known
as a ligand-to-metal charge transfer (LMCT)
transition. Metal-to-ligand-charge-transfer
(MLCT) is also known.

Intensity of colour:
A = cl
A= absorbance
= absorbance coefficient (m2mol-1 )
c = concentration of the solution (mol/L)
l = path length (cm)

The intensity of an electronic transition and hence

the value of is influenced by selection rules.
1. Laporte s.r. : the quantum umber l must
change by +1 or -1 for an electronic
transition t occur. The p->d transition eg.
(l=1 -> l=2). d-d transitions are not allowed
by this rule.
2. Parity s.r.: g->g or (u->u) transitions are
forbidden. This means that t2g to eg
transition for octahedral complex ions is
not allowed. Whereas the e to t2 transition
for tetrahedral is not affected by this rule
and hence the solutions for latter are more
intensely coloured.
3. Spin s.r.: transitions which require spin
reversal are formally forbidden. High spin
octahedral (weak field) complexes
containing d5 metal ion are almost
colourless as electronic transition in these
complexes are forbidden by all 3 of the
rules.
Crystal Field Stabilisation Energy (CFSE)/LFSE
CFSE manifests itself in experimental values of
thermodynamic quantities, L.E., Standard
reduction potential, hydration energies, etc.
octahedral arrangement typically leads to a
higher CFSE than the corresponding
tetrahedral case.
The net effect of the d electrons energy

Magbitude of depends on:

1. number, nature and disposition of ligand
2. nature and o.s. of the metal ion (for a 1st row
transition metal ion a change from a +2 to
+3 o.s. roughly doubles )
3. the period of the periodic table to which the
metal ion belongs (increases going down
the period)
4. the internuclear distance between the metal
ion and the donor atom of the ligand.
As a result of 3. Most complexes containing second
and third row transition metal ions are low spin
and colourless.

Jahn-Teller Distortion
Many octahedral complexes have a distorted
geometry whereby two axial bonds are longer or
shorter than the other four. Distortion from a
regular octahedron is termed tetragonal.
Jahn-teller effect is a manifestation of the
theorem: a non-linear molecule in a degenerate

splitting represents the additional stability

that may be thought to accrue because
crystal field splits the energies of the d
orbitals.

Square planar complexes

Sterically less favoured than tetrahedral, if
the ligands are small enough to adopt a
square planar arrangement then they can
also readily form an octahedral geometry
on steric grounds alone.
Great stabilization of the dz2 orbital relative
to the octahedral case, a smaller
stabilization of the dxz and dyz orbitals and
because the loss of two ligands allows the
remaining four to move closer to the metal
centre, a destabilization of dx2-dy2and dxy
orbitals. The dx2-dy2 has the highest energy
as this is the only orbital that points
directly at the negative point charge
ligands.
Best known for d8, Pt2+ always square
planar, Pd2+nearly always, Ni2+ sometimes.
Energy of stabilization of the complex
increases by 1 when a d8 metal ion adopts
a square planar rather than an octahedral
geometry.
Square planar configuration only occurs
when 1>P. The larger 0, the larger 1
and hence square planar geometry is more
favourable for 2nd and 3rd row d3 metal
ions.

electronic state will be unstable and will undergo a

geometrical distortion which lowers its symmetry
and splits the degenerate state.
If orbitals are unsymmetrically occupied
the resulting repulsion will be
unsymmetrical and hence some ligands will
be able to approach closer to the metal ion
than the others and hence a distorted
geometry.
Largest distortion expected when eg set is
unsymmetrically occupied as these orbital
point directly towards the negative point
charge ligands.
Distortion increases the energy of
stabilization of the octahedral complex.
Largest for h.s. d4, l.s. d7, d9
Linear complexes
Aligned along the z axis which means the
dz2orbital is the highest energy orbital. The
other d orbitals are divided into two pairs of
degenerate orbitals: dxz and dyz and the dx2y2 and dxy orbital, the latter pair being the
lowest in energy.
Typically formed by d10 ions