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INORGANIC CHEMISTRY

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
Band: continuum of energy levels
form N 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
insulators depend on:
band is 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
n-type semiconductors: more valence
few electrons have sufficient thermal
electrons than silicon
energy to be promoted to the empty band
above
p-type semiconductor: less valence
electron than silicon
Semiconductors: band gap not as large;
a few 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) -Ca, Sr, Ba behave just as the 1A group
hence must be stored under oil
-Be does not react with water; Mg only
+
2M (s) + 2 H2O (l) -> 2M (aq) + 2 OH
reacts with steam
(aq) + H2 (g)
-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 Be2+ form compounds that are essentially
with N2
covalent due to its small size
6 Li(s) + N2 (g) -> 2 Li3N (s)
In 3A, B is a metalloid, forms covalent
Despite both being in 4A, C and Si have
molecular compounds (eg. BX3)
different 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
Chlorine is a yellow-green gas
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, 3coordinate 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)

-high reactivity of F is primarily due to the


weak F-F bond; F is a very strong oxidising
agent

-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
2. The cation is often a complex ion,
metals
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 coordination 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
3d10
V-4s2 3d3
Co- 4s2 3d7
Cr-4s1 3d5
Ni-4s2 3d8
Common o.s. :
Sc +3
+7
Ti +2, +3, +4
Cu +1, +2
V +2,+3,+4,+5
Zn +2
Cr +2,+3,+6

Cu-4s1 3d10
Zn- 4s2

Mn +2, +3, +4,


Fe +2, +3
Co +2, +3
Ni +2

Co-ordination Compounds:
Coord
Geometry
no.
6
Octahedral
4
Tetrahedral or square planar
2
Linear
2+
Pt 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

Ionization energies:
Generally increase going across the period
.
I3 increases more rapidly than I1.
Standard reduction potential:
All of the first row transition metal except
copper can reduce H+ ion to hydrogen gas
in 1M solutions of strong acid.
Reducing abilities generally decrease
across the period
Sc>Ti>V>Mn>Cr>Zn>Fe>Co>Ni>Cu (Cr
and Zn do not follow this trend.

Structural isomerism:
1. Ionisation isomerism eg.
CrSO4(NH3)5Br and . CrBr(NH3)5SO4
2. Co-ordination eg. Cu(NH3)4PtCl4
and Pt(NH3)4CuCl4
3. Linkage eg. CoCl(NO2)(NH3)4Cl and .
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.

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

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

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.
Assumes that ligands can be
approximated by negative point
charges and the metal-ligandbonding 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,
None of the d orbitals point towards
MnO4- purple
the point of charge ligands in a
d1 Ti(H2O)63+ purple, VO(H2O)52+ blue
tetrahedral complex.
The t2 set are closer to the negative
d2 V(H2O)63+ blue-green
poin tin charge than the e set. Hence d3 V(H2O)62+ violet, Cr(H2O)63+ violet
the t2 set occur at higher energy.
d4 Cr(H2O)62+ sky blue
t is small hence invariably high

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

spin,
t =4/90
Favoured if the central atom is small
or the ligands large for then the
steric effects override the energy
advantage of forming metal-ligands
bonds.

d6 Fe(H2O)62+ light green


d7 Co(H2O)62+ rose
d8 Ni(H2O)62+ emerald green
d9 Cu(H2O)62+ blue
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-chargetransfer (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)

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.

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 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

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 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 dx2-y2 and
dxy orbital, the latter pair being the
lowest in energy.
Typically formed by d10 ions

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.