CHE 126

Electronic Configuration

Periodicity and building up of the

periodic table

Extraction of metals
Hybridization and shapes of simple
molecules

Comparative chemistry of group IA, IIA

and IVA elements.
•How are the electrons in a given atom
distributed among the various orbitals?
Do they all pile up into just a few
orbitals or do they distribute themselves
more widely?
•How does the expected distribution of
electrons among available orbitals differ
for atoms of different elements?
•To answer these fundamental questions
we need to consider three important rules
or principles governing electronic
configurations.
•The electronic configuration of an atom
is a designation of the distribution of its
electrons among the different electronic
shells and orbitals.
1. Electrons occupy orbitals in such a
way as to minimize the energy of the
atom. The below figure A implies an
order in which electrons occupy orbitals,
first the 1s, then 2s, 2p and so on.
Figure A: The order of filling of
electronic subshells.
Actually, the energy of an atom is not
minimized in most cases just by filling
the principal electronic shells in
succession. At higher quantum numbers
and for certain elements an overlapping
of sublevels occurs, for example, with 4s

filing before 3d in potassium and calcium.

As a result we must establish the order of

filling of orbitals by experiment.

The order obtained is roughly the one
listed below 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p,
5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
Another useful rule is that for any given
pair of orbitals the one with the lower
total number of n and l quantum numbers
fills first. For example, the 3s orbital
(3+0=3) fills before the 3p (3+1=4).
If the n+l totals are the same for two
orbitals, the one with the lower n value
generally fills first. Thus, the 3d orbital
(3+2=5) fills before the 4p (4+1=5).
2. No two electrons in an atom may have
all four quantum numbers alike- the Pauli
Exclusion Principle. In 1926 Wolfgang
Pauli noted that some lines that should
have been present in emission spectra
were not there. He was able to explain
the absence of these lines by stating that
no two electrons in an atom can have all
four quantum numbers alike.
The first three quantum numbers n, l &
ml determine a specific orbital. Two
electrons may have these three quantum
numbers alike,
but if they do they must have different
values of ms, the spin quantum number.
Another way to state this result is that
only two electrons may exist in the same
orbital and these electrons must have
opposite spins.
Because of this limit of two electrons per
orbital, the capacity of a subshell for
electrons can be obtained by doubling the
number of orbitals in the subshell.
Thus, the s subshell consists of one
orbital having a capacity of two electrons;
the p subshell consists of three orbitals
having a total capacity of 6 electrons and
so on.
The capacity of a principal shell is also

twice the number of orbitals it contains

leading to the expression

maximum number of electrons in the

electronic shell with principal quantum

number n=2n2
3. The principle of maximum multiplicity-
Hund's rule. When orbitals of identical
energy (those in the same subshell) are
available, electrons occupy these singly
rather than in pairs.
As a result, an atom tends to have as

many unpaired electrons as possible.

This behaviour can be rationalized by

saying that electrons,

because they all carry the same electric
charge seek out empty orbitals of similar
energy in preference to pairing up with
electrons in half-filled orbitals.
Electronic configurations of the
elements
To apply the principles, it is handy to use
shorthand designations.
The electronic configuration of an atom
of carbon is represented in two different
ways below

spdf notation: C 1s22s22p2

Orbital diagram: C

In each of these designations a total of

six electrons must be assigned since the
atomic number of carbon is 6.
The spdf notation denotes the total
number(the superscript) of electrons in
each subshell. The orbital diagram breaks
down each subshell into individual
orbitals (drawn as boxes) and
indicates the number of electrons for
each orbital. This is done with arrows.
An arrow pointing upward corresponds
to one type of spin(+1/2) and an arrow
pointing down to the other spin (-1/2).
Electrons in the same orbital with
opposing (opposite) spins are said to
be paired. The electrons in the 1s and
2s orbitals of carbon atom are paired.
Electrons with the same type of spin are said
to have parallel spins, as in the 2p orbitals of
carbon. The electronic configuration
described above for carbon is called the
ground-state electronic configuration.
•The electron configuration of an atom can
be written as the numbers of electrons in
each shell, separated by a comma.
The order obtained is roughly the one
listed below 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p,
5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
Another useful rule is that for any given
pair of orbitals the one with the lower
total number of n and l quantum numbers
fills first. For example, the 3s orbital
(3+0=3) fills before the 3p (3+1=4).
for 3s
n=3, l=0 n+l=3+0=3
for 3p
n=3, l=1 n+l=3+1=4
If the n+l totals are the same for two
orbitals, the one with the lower n value
generally fills first. Thus, the 3d orbital
(3+2=5) fills before the 4p (4+1=5).
l=0 for s orbital, l=1 for p orbital, l=2 for
d orbital
To calculate the value for 3d
n=3, l=2 n+l=3+2=5
for 4p n=4, l=1 n+l=4+1=5
2. No two electrons in an atom may have
all four quantum numbers alike- the Pauli
Exclusion Principle. In 1926 Wolfgang
Pauli noted that some lines that should
have been present in emission spectra
were not there. He was able to explain
the absence of these lines by stating that
no two electrons in an atom can have all
four quantum numbers alike.
The first three quantum numbers n, l &
ml determine a specific orbital. Two
electrons may have these three quantum
numbers alike,
but if they do they must have different
values of ms, the spin quantum number.
Quantum number
The principal quantum number (n), the
orbital angular momentum quantum
number (l), the magnetic quantum
number (ml), and the electron spin
quantum number (ms).
The Ground-state electronic configuration
is the most probable or the most energetically
favoured configuration.
The Aufbau process
Consider the following hypothetical process-
the building up of more complex atom
starting with the simplest atom, hydrogen.
This hypothetical process is called Aufbau
process (meaning building up in German)
In this process we proceed from an atom
of one element to the next by adding a
proton and the requisite number of
neutrons to the nucleus and one electron
to the appropriate orbital. We pay
particular attention to this added
electron, called the differentiating
electron.
Hydrogen, Z =1. The lowest energy
state for the electron in a hydrogen
atom is the 1s orbital. The electronic
configuration is 1s 1
Helium, Z =2. In the helium atom a
second electron goes into the 1s orbital.
The two electrons must have opposing
spins, 1s2.
Lithium Z=3.

The differentiating electron cannot be

accommodated in the 1s orbital (Pauli
exclusion principle). It must be placed in
the next lowest energy orbital 2s. The
electron configuration is 1s22s1

Beryllium Z=4
 SUMMARY
•Electrons in an atom are located in
defined regions called electron shells,
which surround the nucleus.
•This arrangement of electrons is referred
to as the electron configuration.
•There are ‘rules’ which determine how
electron shells are filled, and how many
electrons they can contain:
•Inner shells begin filling first; they are
smaller and can hold less electrons.
•A maximum of 2 electrons can occupy
the first shell.

•A maximum of 8 electrons can occupy

the second shell.
•A maximum of 18 electrons can occupy
the third shell, but the fourth shell will
begin to fill once the third shell contains
8 electrons.
•A maximum of 8 electrons can occupy
the valence shell (outermost shell) of any
atom, unless the valence shell is the only
shell, in which case there can be a
maximum of 2 electrons. The electron
configuration of an atom can be written as
the numbers of electrons in each shell,
separated by a comma.
•
•
Periodicity
Periodicity refers to trends
or recurring variations
in element properties with
increasing atomic number.
Periodicity is caused by
regular and predictable
variations in element atomic
structure.
Mendeleev organized
elements according to
recurring properties to make a
periodic table of elements.
Elements within a group
(column) display similar
characteristics. The rows in the
periodic table (the periods)
reflect the filling
of electrons shells around the
nucleus, so when a new row
begins, the elements stack on

top of each other with similar

properties. For example,
helium and neon are both
fairly unreactive gases that
glow when an
electric current is passed
through them. Lithium and
sodium both have a +1
oxidation state and are
reactive, shiny metals.
• Elements were first arranged
in order of increasing atomic
weight by Dimitri
Mendeleev. He observed that
elements with similar
properties appeared
periodically at regular
intervals. The earliest
version of the
periodic table was
constructed so that elements
with similar properties fell
into vertical columns.
In the modern form of the
periodic table, elements are
arranged in order of
increasing
atomic numbers (i.e. the
number of protons in the
atom).
The periodic table illustrates
the periodic law. When
elements are arranged in
ascending atomic
number, similar chemical and
physical properties recur
periodically.
• The reason why the properties
of elements are related
periodically to their atomic
numbers is that,
the atomic number of an
element determines its
electronic configuration,
which in turn determines its
atomic properties (like atomic
radius, ionization enthalpy,
electronegativity e.t.c.).
Furthermore, the atomic
properties directly affect the
type of bonding and structure
of the element.
The periodic table is divided
into 7 horizontal rows and 8
vertical columns. The
horizontal rows are called
periods which are numbered
from the top downwards
(period 1, period 2,………
period 7). Elements in the
same period have the same
number of occupied electron
shell(s).

The vertical columns are

called groups and they are
numbered from left to right
(Group 1A, IIA,…….Group 0).
Elements in a particular group
have the same number and
arrangement of the outermost
shell electron(s).
• The periodic table can also be
divided into four blocks
namely, s-, p-, d-, and f-
blocks .
S-block

Group IA and IIA elements form

the s-block as their outermost
shell electrons are located in the
s-subshell.
P-block
Elements of groups IIIA to O are
known as p-block elements. It is
because of their outermost shell
electrons are located in the p-
subshell.
Elements in the s- and p- blocks
are known collectively as the
representative elements.
However, this is not applicable
to elements in group O. They are
called noble gas elements.
D-block

D-block elements have their

highest energy electrons in the
inner d-subshell. They are also
called transition elements.
F-block

F-block elements have

electrons filling the inner f-
subshell. There are two series
of f-block elements, the
lanthanide series {Z=58-71}
and actinide series {Z= 90-
103}. They are also called the
inner-transition elements.
Uses of Periodicity
Periodicity was helpful to
Mendeleev because it showed
him gaps in his periodic table
where elements should be.
This helped scientists find
new elements because they
could be expected to display
certain
characteristics based on the
location they would take in the
periodic table.
Properties That Display
Periodicity
Periodicity can include many
different properties, but the
key recurring trends are:
Ionization Energy - This is
the energy needed
to completely remove an
electron from an atom or ion.
Ionization energy increases
moving left to right across the
table and decreases moving
down a group.
Electronegativity- A
measure of how readily an
atom forms a chemical
bond.
Electronegativity increases
moving left to right across a
period and decrease moving
down a group.
• Atomic Radius- This is half
the distance between the
middle of two atoms just
touching each other.
Atomic radius decreases
moving left to right across a
period and increases moving
down a group.
• Moving Left → Right
• Ionization Energy Increases
• Electronegativity Increases
• Atomic radius Decreases
• Moving Top → Bottom
• Ionization Energy Decreases
• Electronegativity Decreases
• Atomic Radius Increases
Periodic Properties
Some of the Periodic
Properties that are influenced
directly by the electron
configuration:
Atomic size
The size of atoms increases
going down in the periodic
table but decreases from left to
right across a period.
There is addition of shell(n) as
we go down the group but as
we go across the period, more
protons are being added to the
nucleus
and more electrons to the
valence shell of the element.
The electronic configuration
explains why there is a
decrease from left to right
across a period. What is not
changing as you cross a period
is the inner shell electrons.
The inner shell electrons are a
shield against the pull of the
nucleus. As you cross a period
and increase the number of
protons in the nucleus you
increase its pull but since you
are only adding electrons to the
new shell, the shield is not
increasing but remains the
same all the way across.
This means the pull on the
electrons being added to the
valence shell is increasing
steadily all the way across.
What happens if you pull
harder on the electrons? Well,
they come closer to the
nucleus and the size of the
atom decreases.
The effect of the nucleus
pulling on the electrons being
added across a period is called
the effective nuclear charge.
Electronegativity

Electronegativity is an atom’s
ability to pull electrons towards
itself.
The electronegativity values
increase from left to right and
bottom to top in the periodic
table excluding the Noble
gases.
The most electronegative
element is Fluorine.
Ionization Energy

Ionization energy is the amount

of energy required to remove
an electron from an atom.
The more electronegative the
element, the higher the
ionization eneregy.
Electron Affinity

The Electron Affinity of an

element is the amount of
energy gained or released with
the addition of an electron. The
electronegativity and Electron
Affinity increase in the same
pattern in the periodic table.
 Group one-The Alkali metals

Element Symbol Electronic Structure

Lithium Li 1s22s1
Sodium Na 1s22s22p63s1
Potassium K 1s22s22p63s23p64s1
Rubidium Rb 1s22s22p63s23p64s24P65s1
Caesium Cs
1s22s22p63s23p64s24P65s15P66s1
Francium Fr [Rn]7s1
Occurrence and Abundance
Despite their close chemical
similarity, the elements do not
occur together, mainly
because their ions are of
different size. Sodium is the most
abundant, followed by potassium,
rubidium, lithium, and caesium.
Francium is intensely radioactive
and very rare.
 Lithium is the thirty-fifth most
abundant element by weight
and is mainly obtained as the
silicate minerals,
•
spodumene LiAl(SiO3)2 and
lepidolite
Li2Al2(SiO3)3(FOH)2.
• Sodium and potassium are the
seventh and eighth most
abundant elements by weight
in the earth’s crust.
The largest source of sodium
is rock salt (NaCl).
Various salts including NaCl,
Na2B4O7.10H2O (borax),
NaNO3 (saltpetre) and
Na2SO4
(mirabilite) are obtained from
deposits formed by the
evaporation of ancient seas.
Potassium occurs mainly as
deposits of KCl (sylvite), a
mixture of KCl and NaCl
(Sylvinite), and the double salt
KCl.MgCl2.6H2O (carnalite).
There is no convenient source
of rubidium and only one of
caesium and these elements are
obtained as by-products from
lithium processing.
• All of the elements heavier than
bismuth (atomic number 83)

83Bi are radioactive.

• Thus francium (atomic number

89) is
radioactive and has a short
half-life period of 21 minutes
it does not occur appreciably
in nature.
 Extraction of metals
• The metals may all be
isolated by electrolysis of a
fused salt, usually the fused
halide, often with impurity
added to lower the melting
point.

Sodium is made by the

electrolysis of a molten
mixture of about 40% NaCl
and 60%CaCl2 in a Downs

cell. This mixture melts at

about 600C compared with

803C for pure NaCl.

The small amount of calcium
formed during the electrolysis
is insoluble in the liquid
sodium, and dissolves in the
eutectic mixture.
• There are three advantages to
electrolyzing

• It lowers the melting point

and so reduces the fuel bill.
The lower temperature results
in a lower vapour pressure for
sodium, which is important as
sodium vapour ignites in air.
• At lower temperature the
liberated sodium metal does
not dissolve in the melt, and
this is important
• because if it dissolved it would
short-circuit the electrodes and
thus prevent further
electrolysis.

• A Downs cell comprises a

cylindrical steel vessel lined

with firebrick, measuring

about 2.5m in height and

1.5m in diameter.
• The anode is a graphite rod in
the middle, and is surrounded
by a cast steel cathode.

• A metal gauze screen separates

the two
electrodes, and prevents the Na
formed at the cathode from
recombining with Cl2 produced
at the anode.
The molten sodium rises, as it
is less dense than the
electrolyte, and it is collected
in an inverted trough
 and removed, and packed into
steel drums.
• A similar cell can be used to
obtain potassium by
electrolyzing fused KCl.
However, the cell must be
operated at a higher
temperature because the
melting point of KCl is
higher, and this results in the
vapourization of the liberated
potassium Since sodium is a
more powerful reducing agent
than potassium and is readily
available, the modern method
is to reduce molten KCl with
sodium vapour at 850 C in a
large fractionating tower.
This gives K of 99.5% purity.
Na +KCl →NaCl +K

Rb and Cs are produced in a

similar way by reducing the
chlorides with Ca at 750C
under reduced pressure.
All react with water to give
hydrogen gas and the metal
hydroxide. They also react
with the oxygen in the air to
give either an
oxide, peroxide or superoxide
depending on the metal.

These metals almost always

form ions with a positive (+1)
charge.
• Most of the alkali metals glow
with a characteristic colour
when placed in a flame;
lithium is crimson, sodium
gives off an intense yellow,
potassium is Lilac, rubidium is
a red-violet, and caesium gives
off blue light.
Electronic structure

Group 1 elements all have one

valence electron in their outer
orbital- an s electron, which
occupies a spherical orbital.
The single valence electron is a
long distance from the nucleus,
is only weakly held and is
readily removed.
In contrast the remaining

electrons are closer to the

nucleus, more tightly held,

and are removed only with

great difficulty.
Because of similarities in the
electronic structures of these
elements, many similarities in
chemical behaviour would be
expected.
 Size of atoms and ions

Group 1 atoms are the

largest in their periods in the
periodic table.
When the outer electron is
removed to give a positive ion,
the size decreases
considerably.
There are two reasons for this.

1). The outermost shell of

electrons has been completely

removed.
2). Having removed an electron,

the positive charge on the

nucleus is now greater than

the charge on the remaining

electrons, so that each of the
remaining electrons is attracted
more strongly towards the
nucleus. This reduces the size
further.
• Positive ions are always
smaller than the parent atom.
Even so, the ions are very
large, and they increase in
size from Li+ to Fr+ as extra
shells of electrons are added.
The Li + is much smaller than
the other ions. For this reason,
Li only mixes with Na above
380°C and it is immiscible
with the metals K, Rb and Cs,
even when molten.

In contrast the other metals Na,

K, Rb and Cs are miscible with
each other in all proportions.
Density
The atoms are large, so group
1 elements have remarkably
low densities.
 Metallic Ionic Density
radius radius (gcm-3)
(Å) M+(Å)

Li 1.52 0.76 0.54

Na 1.86 1.02 0.97
K 2.27 1.38 0.86
Rb 2.48 1.52 1.53
Cs 2.65 1.67 1.90
Ionization Energy
• The first ionization energies
for the atoms in this group are
appreciably lower than those
for any other group in
the periodic table. The atoms
are very large so the outer
electrons are only held weakly
by the nucleus.
• Hence the amount of energy
needed to remove the outer
electron is not very large.
• On descending the group from

Li to Na to K to Rb to Cs, the

size of the atoms increases; the

outermost electrons become

less strongly held, so the
ionization energy decreases.
Electronegativity
The electronegativity values
for the elements in this group
are very small- in fact the

smallest values of any

element. Thus when these

elements react with other

elements to
form compounds, a large
electronegativity difference
between the two atoms is
probable, and ionic bonds are
formed.
Li- 1.0, Na-0.9, K-0.8,
Rb-0.8, Cs-0.7(Pauling’s
electronegativity).
Chemical properties
Some reactions of Group 1
metals
2M +2H2O →2MOH +H2
The hydroxides are the
strongest bases known.
With excess dioxygen
4Li +O2 →2Li2O
Monoxide is formed by Li and
to a small extent by Na.
 2Na+O2→Na2O2
Peroxide is formed by Na and to
a small extent by Li

K +O2 →KO2 Superoxide

formed by K, Rb, Cs.
• 2M +H2 →2MH ionic
‘salt-like’ hydrides.
• 6Li +N2 →2Li3N Nitride
formed only by Li.
• 3M +P →M3P All the
metals form phosphides
• 3M +As →M3As All the
metals form arsenides

• 3M +Sb →M3Sb All the

metals form stibnides
• 2M +X →M2X (X=S,Se,Te)
All the metals form
sulphides, selenides, and
tellurides.
• 2M +X2 →2MX (X=F, Cl, Br, I)
All the metals form fluorides,
chlorides, bromides, and
iodides
• 2M + 2NH3 →2MNH2 + H2
All the metals form amides
 Uses of Lithium:

• Lithium is used to make

electrochemical cell (both
primary and secondary
batteries).
Lithium is used in lubricants,
in glass industries, and in
alloys of lead, aluminum, and
magnesium to make them less
dense and stronger.
Uses of sodium:

Liquid sodium metal is used as

a coolant in fast breeder
nuclear reactor. Sodium nitrite
is a principal
ingredient in gunpowder. The
pulp and paper industry uses
large amounts of sodium
hydroxide, sodium carbonate,
and sodium sulphate.
• Sodium carbonate is used by
power companies to absorb
sulfur dioxide, a serious
pollutant, from smokestack
gases (locomotive chimneys or
ship chimneys). Sodium
carbonate is also used in
the glass and detergent
industries.
Sodium chloride is used in
foods and to soften the water.

Sodium bicarbonate (baking

soda) is used in the food
industry as well.
 Uses of potassium:

• Potassium is an essential
element for life. Roughly 95%
of Potassium compounds are
used as fertilizers for plants.
• Potassium hydroxide is used in
detergent.

• Potassium chlorate is used in

explosive.
• Potassium carbonate is used
in ceramics, colour TV tubes
and fluorescent light tubes.

Potassium bromide is used in

photography industries.
Uses of Rubidium and

caesium:

Rubidium is used almost

exclusively for research, but.

caesium is used in special
glasses and radiation detection
equipment
GROUP TWO-THE ALKALINE EARTH
METALS
Element Symbol Electronic Structure
Beryllium Be 1s22s2
Magnesium Mg 1s22s22p63s2
Calcium Ca 1s22s22p63s23p64s2
Strontium Sr
1s22s22p63s23p63d104s24p65s2
Barium Ba
1s22s22p63s23p63d104s24p64d105s25p66s2
Radium Ra [Rn]7s2
Alkaline earth metals make up
the second group of the
periodic table.

• This family includes the

elements beryllium,
• magnesium, calcium,
strontium, barium, and radium
(Be, Mg, Ca, Sr, Ba, and Ra,
respectively).
• These metals are silver and
soft, much like the alkali
metals of Group 1.
• Each alkaline earth metal has
two valence electrons.
• They will easily give these
electrons up to form cations.
These metals become
increasingly more reactive as
you go down the periodic
• table. This is concurrent with
general periodic trends.
• The group two elements show
the same trends in properties as
were observed with Group 1.
However, beryllium stands

apart from the rest of the

group and differs much more

from them than lithium does

from the rest of Group 1.

The main reason for this is
that the beryllium atom and
Be2+ are both extremely
small, and the relative
increase in size from Be 2+ to
 2+
Mg is four times greater than
the increase between Li+ and
+
Na . Beryllium and barium
compounds are all very toxic.
• The elements form a well-
graded series of highly reactive
metals, but are less reactive
than Group 1.
• They are typically divalent
• and generally form
colourless ionic compounds.

• The oxides and hydroxides

are less basic than those of
Group 1: hence their
oxosalts (carbonates, sulphates,
nitrates) are less stable to heat.
Occurrence and Extraction
These elements are all found in
the Earth’s crust, but not in the
the elemental form as they are
so reactive. Instead, they are
widely distributed in rock
structures.
• Beryllium, like its neighbours
Li and B is relatively not very
abundant in the earth’s crust.
• It occurs to the extent of
about 2ppm and is thus
similar to Sn (2.1 ppm), Eu
(2.1 ppm) and As (1.8
ppm).
• Beryllium is found in small
quantities as the silicate
minerals beryl Be3Al2Si6O18
and phenacite Be2SiO4.
Magnesium is the sixth most
abundant element in the
earth’s crust (27640 ppm ).

The main minerals in which

magnesium is found are
carnellite (KCl.MgCl2.6H2O),
magnesite (MgCO3) and
dolomite (MgCO3.CaCO3).
Calcium is the fifth most
abundant element in the
earth’s crust. Hence the
third most abundant metal
after Al and Fe.
Calcium is found in gypsum
(CaSO4.2H2O), anhydrite
(CaSO4), fluorite (CaF2),
apatite (Ca5(PO4)3F) and
limestone (CaCO3).There are
two crystalline forms of
CaCO3, calcite and aragonite
Strontium (384ppm) and
barium (390ppm) are much
less abundant, but are well
known because they occur as
concentrated ores, which are
easy to extract. They are
respectively the fifteenth and
fourteen element in abundance.
Strontium is mined as celestite
SrSO4 and strontianite
(SrCO3).
Ba is mined as Barytes BaSO4.
Radium is extremely scarce
and is radioactive. It was first
isolated by Pierre and Marie
Curie by processing many tons
of the uranium ore pitchblende.
Of the elements in this Group
only magnesium is produced
on a large scale.
It is extracted from sea-water
by the addition of calcium
hydroxide, which precipitates
out the less soluble magnesium
hydroxide.
This hydroxide is then
converted to the chloride,
which is electrolysed in a
Downs cell to extract
magnesium metal.
The metals of this group are
not easy to produce by
chemical reduction because
they are themselves strong
reducing agents, and they
• The metals of this group are
not easy to produce by
chemical reduction because
they are themselves strong
reducing agents, and they
• react with carbon to form
carbides. They are strongly
electropositive and react with
water, and so aqueous
solutions cannot be used for
displacing them with another
metal, or for electrolytic
production. All the metals can
be obtained by electrolysis of
the fused chloride, with
• sodium chloride added to
lower the melting point,
although strontium and
barium tend to form a
colloidal suspension.
 Properties of the elements
• The alkaline earth metals are
silvery white, lustrous and
relatively soft. Their physical
properties when compared with
• those of group 1A metals,
show that they have a
substantially higher melting
point., boiling point, enthalpies
of fusion and vapourization.
• They have two valency
electrons which may
participate in metallic bonding,
compared with one electron for
Group 1 Metals.
Consequently Group 2
metals are harder, have
higher cohesive energy and
much higher melting points
and boiling points than
Group 1 elements. The melting
points do not vary regularly,
mainly because the metals
adopt different crystal
structures.
Melting points of Group 1 and
2
Melting Pt(°C)
Be 1287 Li 181
Mg 649 Na 98
Ca 839 K 6
Sr 768 Rb 39
Ba 727 Cs 28.5
This can be understood in
terms of the size factor and the
fact that two valency electrons
per atom are now available for
bonding.
Again, Be is notable in
melting more than 1100°C
above Li and being nearly 3.5
times as dense; its enthalpy of
fusion is more than 5times that
of Li.

Size of atoms and ions

Group 2 atoms are large but are

smaller than the corresponding
group 1 elements as the extra
charge on the nucleus draws the
orbital electrons in. Similarly the
ions are large, but smaller than
those of Group 1, especially
because of the removal
of two orbital electrons
increases the effective nuclear
charge further. Thus, these
elements have higher densities
than group 1 metals.
 Size and Density
metallic Ionic Density
radius(Å) Radius(Å) (gcm-3)
Be 1.12 0.31 1.85
Mg 1.60 0.72 1.74
Ca 1.97 1.00 1.55
Sr 2.15 1.18 2.63
Ba 2.22 1.35 3.62
Ra 1.48 5.5
Comparison with group 1A
shows the substantial increase in
the ionization energies; this is
related to their smaller size and
higher nuclear charge and is
particularly notable for Be.
Ionization energy
1st 2nd 3rd
Be 899 1757 14847
Mg 737 1450 7731
Ca 590 1145 4910
Sr 549 1064
Ba 503 765
Ra 509 979
• The third ionization energy is
so high that M3+ ions are
never formed. The ionization
energy for Be 2+ is high and its
compounds are typically
covalent, Mg also forms some
covalent compounds.

However, the compounds

formed by Mg, Ca, Sr and Ba
are predominantly divalent and
• ionic. Since the atoms are
smaller than those in Group 1,
the electrons are more tightly
held so that the energy needed
to remove the first electron
• (1 st ionization energy) is
greater than those in Group 1.
Once one electron has been
removed, the ratio of charges
on the nucleus to
orbital electrons is increased,
so that the remaining electrons
are more tightly held. Hence
the energy needed to remove a
second electron is nearly
double that required for the
first.
ELECTRONEGATIVITY

The electronegativity values of

Group 2 elements are low, but
are higher than the values for
Group 1.
The electronegativity difference
between Group 2 metals(Mg,
Ca, Sr, and Ba) and the halogens
or oxygen is large and the
compounds are ionic.
The value for Beryllium is higher
than for others.
HYDRATION ENERGIES
The hydration energies of the
Group 2 ions are four or five
times greater than for group 1
ions. This is largely due to
their smaller size and
increased charge. The
crystalline compounds of
Group 2 compounds contain
more water of crystallization
than the corresponding Group
1 compounds.
Thus NaCl and KCl are
anhydrous but MgCl2.6H2O,
CaCl2.6H2O and
BaCl2.2H2O all have water
of crystallization. .
Note that the number of
molecules of water of
crystallization decreases as the
ions become larger
Differences between
Beryllium and the other
Group 2 elements

Beryllium is anomalous in
many of its properties and
shows diagonal relationship to
aluminum in Group 3.

It is extremely small and has a

high charge density and so by
Fajans rules it
has a strong tendency to
covalency. Beryllium hydride is
electron deficient and polymeric
with multicentre bonding like
aluminium hydride.
• The halides of beryllium are
electron deficient, and
polymeric with halogen
bridges. BeCl2 usually forms
chains but also exists as the
dimer. AlCl3 is dimeric.
Be forms many complexes –
not typical of Groups 1 and 2.
Be like Al is rendered passive
by nitric acid.
Be is amphoteric, liberating
H2 with NaOH and forming
beryllates. Al forms
Aluminates.

Be(OH)2 like Al(OH)3 is

 amphoteric.
• Be salts are extensively
hydrolysed.
• Be salts are among the most
soluble known.
• Beryllium forms an unusual

carbide Be2C which like

Al4C3 reacts with water to

give methane whereas

• magnesium carbide and calcium
carbide give propyne and
ethyne(formerly called
acetylene) respectively.
Be2C+4H2O → 2Be(OH)2 + CH4

Mg2C3 + 4H2O → 2Mg(OH)2 +

C3H4

CaC2 + 2H2O → Ca(OH)2 +

C2H2
Beryllium metal is relatively

unreactive at room

temperature, particularly in

its massive form.

It does not react with water or
steam even at red heat and does
not oxidize in air below 600°,

though powdered Be burns

brilliantly on ignition to give
BeO and Be3N2.

The halogens (X2) react

above 600°C to
give BeX2 but the chalcogens
(S, Se, Te) require higher
temperatures to form BeS,
e.t.c.
• Ammonia reacts above 1200°C
to give Be3N2 and carbon forms
Be2C at 1700°C.
In contrast with the other
group IIA metals, Be does
not react directly with
Hydrogen, and BeH2 must be
prepared indirectly.
Cold concentrated HNO3
passivates Be but the metal
dissolves readily in dilute
aqueous acids (HCl, H2SO4,
HNO3) with the evolution of
hydrogen. Beryllium is sharply
distinguished from the other
alkaline earth metals in
reacting with aqueous
alkalis(NaOH, KOH) with
evolution of hydrogen.
Magnesium is more
electropositive than the
amphoteric Be and reacts more
readily with most of the
non metals. It ignites with the
halogens, particularly when they
are moist, to give MgX2 and
burns with dazzling brilliance in
air to give MgO, Mg3N2.
It also reacts directly with the
other elements in Group V
and VI (and Group IV); when
heated and even forms MgH2
with hydrogen at 570 and 200
atm. Steam produces MgO, or
Mg(OH)2 plus Hydrogen and
ammonia reacts at elevated
temperature to give Mg3N2.
• The heavier alkaline earth
metals, Ca, Sr, Ba (and Ra)
react even more readily with
non metals and again the
direct formation of nitrides M3N2
is notable. Other products are
similar though the hydrides are
more stable and the carbides less
stable than for Be and Mg.
• There is also a tendency,
previously noted for the
alkali metals to form
peroxides MO2 of increasing
stability in addition to the
normal oxides MO.
Some reactions of Group 2
metals
M +2H2O →M(OH)2 +H2
Mg with hot water, and Ca,
Sr and Ba react rapidly with
cold water.
1. 2M +O2 →2MO
Normal oxide formed by
all group members.
With excess dioxygen
• Ba +O2 →BaO2 Ba
also forms the peroxide.
 M +H2 →MH2
Ionic ‘salt–like’ hydrides
formed at high temperatures
by Ca, Sr and Ba.
3M +N2 →M3N2
All form nitrides at high
temperatures.
3M +2P →M3P2 All the
metals form phosphides at
high temperatures.

M +X →MX (X=S, Se,Te)

All the metals form
 sulphides, selenides, and
tellurides.
M +X2 →MX2 (X=F, Cl,Br, I) All
the metals form fluorides,
chlorides, bromides and iodides.
M +2NH3 →M(NH2)2 + H2

All the metals form amides at

high temperatures.
Hydroxides

Be(OH)2 is amphoteric, but

the hydroxides of Mg, Ca, Sr
and Ba are basic.
• The basic strength increases
from Mg to Ba and Group 2
shows the usual trend that
basic properties increase on
descending a group.
SULPHATES
The solubility of the sulphates
in water decreases down the
group, Be  Mg  Ca  Sr 
Ba.
Thus BeSO4 and MgSO4 are
soluble but CaSO4 is
sparingly soluble and the
sulphates of Sr, Ba and Ra
are virtually insoluble.
• The significantly higher
solubilities of BeSO4 and
MgSO4 are due to the high
enthalpy of solvation of the
smaller Be2+ and Mg2+ ions.
The sulphates all decompose
on heating, giving the oxides:
heat
MgSO4 → MgO+SO3
• MgSO4 and CaSO4 cause
permanent hardness in water
while the presence of Mg(HCO3)2
and Ca(HCO3)2 causes temporary
hardness in water.
 HYDRIDES

The elements Mg, Ca, Sr and

Ba all react with hydrogen to
form hydrides MH2.
Beryllium hydride is difficult
to prepare, and less stable than
the others.
Hydrides are all reducing
agents and are hydrolysed by
water and dilute acids with the
evolution of hydrogen.

CaH2 +2H2O→Ca(OH)2+2H2
NITRIDES

The alkaline earth elements all

burn in dinitrogen and form

ionic nitrides M3N2.

This is in contrast to Group 1

where Li3N is the only nitride

formed.

3Ca +N2 →Ca3N2

All the nitrides are all
crystalline solids, which
decompose on heating and
react with water, liberating
ammonia and
forming either the metal oxide or
hydroxide e.g.

• Ca3N2 +6H2O →3Ca(OH)2 +2NH3

Compounds

The predominant divalence of

the GroupIIA metals can be

interpreted in terms of their

electronic configuration,
ionization energies and size.
Further ionization to MX3 is
impossible[14847kJmol -1 for
Be, 7731kJmol-1 for Mg and
-1
4910kJmol for calcium].
Univalent compounds are non
existent due to higher
enthalpy of formation of MX2
which leads to rapid and
complete disproportionation
of MX. The standard enthalpy
of formation of MgCl,
assuming the NaCl structure is
-125kJ/mol, which is
substantially greater than for
many known stable compounds
and essentially the same as the
experimentally observed value
for AgCl.
 USES

• In its elemental form,

magnesium is used for
structural purposes in car
engines,
pencil sharpeners, and many

electronic devices such as

laptops and cell phones.

In a biological sense,
magnesium is vital to the

body's health: the Mg 2+ ion is a

component of every cell type.

• Calcium metal is used to
make alloys with
Aluminium for bearings.

It is used in the iron and

steel industry to control
carbon in cast iron and as a
scavenger for P, O and S.
Other uses are as a reducing agent
in the production of other metals-
Zr, Cr, Th and U- and for
removing traces of N2 from argon.
Chemically CaH2 is

sometimes used as a source

of H2. Radium was used for

radiotherapy
treatment of cancer at one

time: other forms of

radiation are now used.

INTRODUCTION TO NUCLEAR CHEMISTRY

•Electrons
•physical and chemical properties of atoms,
ion, molecules etc, in every day life
•Nuclear chemistry
•phenomena in the nuclei of atoms

1
INTRODUCTION TO NUCLEAR CHEMISTRY
• mass and energy are equivalent &
interconvertible
• law of conservation of mass-energy-
“the total of the mass and energy of the
universe is a constant”
• Albert Einstein (1905)
E = mc2 (1J = 1kg M2s-2 )
• i.e every energy change must be accompanied by
change in mass (ΔE=Δm x c2)

2
 MASS DEFECT
• Evidence – Sum of the masses of individual
neutrons, protons and electrons always
greater than the mass of the atom
• missing mass = NUCLEAR BINDING ENERGY
(energy that would be released in the combination of
nucleons to form nucleus)
– energies in nuclear processes, 1 Mev=1.6021892 x 10-13J

• binding energy per nucleon = nuclear binding

energy (nucleus)/no of nucleons in nucleus
– useful for comparing one nucleus with another

3
 MASS DEFECT
Atomic mass of 3919K is 38.96371u.
Calculate the binding energy for this nuclide (n =
1.008665u, p = 1.007276u, e = 0.00054858u, c =
2.9979 x 108 ms-1 and 1u = 1.6605655 x 10-27 kg).
Calculate the total binding energy of one mole of
39 K atoms.
19
 In 3919K there are 19 protons, 20 neutrons and 19
electrons
(19 x 1.007276) + (19 x 0.00054858) + (20 x
1.008665) = 39.32197u
• Mass defect = actual mass – calculated mass
= 38.96371 – 39.32197 = - 0.35826u
4
 MASS DEFECT (Cont.)
• This loss of mass is equivalent to (- 0.35826 x
1.6605655 x 10-27) = - 5.9493 x 10-28 kg
• Energy equivalent of this mass = mc2
= (- 5.9493 x 10-28)( 2.9979 x 108)2
= -5.3469 x 10-11 J
• For 1mole, total binding energy is
this energy x Avogadro number
i.e. (-5.3469 x 10-11)(6.022 x 1023)
= -3.2199 x 1013 J mol-1

5
 binding energy per nucleon
• increases rapidly for lighter elements
– as no of nucleons increases, the nucleons are held
together more strongly
– curve occurs @ Fe (nucleons are most strongly
bound together)
• Nuclear fusion
combination of two light nuclei = heavier
nucleus
– closer to the region of stability, releasing energy.

8
 binding energy per nucleon
• Fission
splitting of heavy nucleus = two lighter nuclei
– releasing energy & hence more stable
both fusion & fission
– nuclei transformed into other nuclei where
nucleons are more strongly bound together

9
 RADIOACTIVITY
• spontaneous emission by unstable nuclei
–particles or electromagnetic radiation
or both
• radio isotopes or radioactive nuclides
• “Natural” refers to substances that occur
naturally on earth

10
 RADIOACTIVITY
• “artificial” – man-made
• Approx. 33% of the elements has
natural radionuclides
–All known isotopes of elements
heavier than Bismuth (Z>83) are
radioactive

11
 RADIOACTIVITY
• Artificial radionuclides
(more than 350)
– nuclear bombs testing (1955-62)
–operation of nuclear power plants
–research laboratories and facilities like
hospitals

12
 RADIOACTIVITY
• Nuclear Reactions
– Spontaneous decay of radioactive nuclides
– Bombardment reactions
• electromagnetic radiation or fast moving
particles captured to form an unstable nucleus
that decays
– Fission of unstable heavy nuclei
– Fusion of light nuclei
• occurs naturally only in the sun and other stars

13
 RADIOACTIVITY
• 1st natural transmutation of an element
(Rutherford and Soddy 1902)

226 Ra
88  4 He
2 + 222 Rn
86

• 1st artificial (Rutherford 1919)

14N
7  4He
2  17O
8 + 1p
1

14
 RADIOACTIVITY

• Discovery of the neutron

(Chadwick 1932)

9Be
4 + 4He
2  12C
6 + 1n
0

conservation of mass number & nuclear

change in both reactants and products

15
 SPONTANEOUS RADIOACTIVE DECAY
γ-decay
• Radioactive decay sometimes leaves nucleus at
unstable excited nuclear energy level, emission of
γ-rays  ground state nuclear energy level
(excess energy electron magnetic radiations)

AX *
Z  AX
Z + 0 γ0

This takes place within a nanosecond following

particle emission.

16
 SPONTANEOUS RADIOACTIVE DECAY
α-decay
• Emission of α- particle by radionuclide
AX
Z  A-4 X
Z-2 + 4He
2

• Heavy nuclides with low neutron-proton ratio

and those with Z >83 undergo α-decay e.g.

185 Au
79  181 Ir
77 + 4 He
2

17
 SPONTANEOUS RADIOACTIVE DECAY
α-decay
– 185
79 Au
(106/79 = 1.34) with 79p and mass no of
185 or 106n lies below stability band and the
product nuclide with 77p & 104n is closer to the
band and hence more stable (104/77 = 1.35).
• α-particle emission leaves nuclide in an
excited state, then γ -radiation is emitted to
reach stable state. Total energy of emitted α-
particle + γ-radiation is equal to the rxn
energy.
18
 SPONTANEOUS RADIOACTIVE DECAY
β-decay - Electron emission (n  p)
(1/0n  1/1p + 0/-1e)
no change in mass no but increases +ve charge by 1

Net effect - conversion of neutron to proton

A/ X  A/ Y + 0/ e
z Z+1 -1

• n/p ratio decreases

• most common mode of decay for radioactive
nuclides since they lie above stability band (too
many neutrons) e.g.
14/ C  14/ N + 0/ e
6 7 -1

19
 SPONTANEOUS RADIOACTIVE DECAY
• β- decay – Positron emission (p  n)
(1/1p  1/0n + 0/+1e)
positron = electron, except +1 instead of
–1, causes decrease of 1 in atomic no but
no change in mass number
A/ X  A/ Y + 0 / e
z Z-1 +1
• increases n/p ratio, isotopes with too
many protons (below stability band)
decay by this process
20
 SPONTANEOUS RADIOACTIVE DECAY
• β- decay – Positron emission (p  n)
• Only artificial radionuclides have been
observed to undergo position emission
• When positron and electron interact,
they annihilate each other –
• all their masses converted to energy
• (two 0.51 meV traveling in opposite
directions)

21
 SPONTANEOUS RADIOACTIVE DECAY
• β- decay – Electron capture (p  n)
(1/1p + 0/-1e  1/0n)
positive charge of an unstable nucleus can be
decreased by electron capture
capture by nucleus of one of its own orbital
electrons
Proton captures an electron to produce
neutron

22
 SPONTANEOUS RADIOACTIVE DECAY
• β- decay – Electron capture
As electrons rearrange themselves to
compensate for the electron pulled into the
nucleus, x-rays are emitted.

A/ X
z + 0/ e
-1  A/ Y
Z-1

202/ Tl
81  202/80Hg (followed by x-rays)
50/ V
23 + 0/-1e  50/22Ti + x-rays.
23
BAND OF STABILITY (NEUTRON/PROTON RATIO)
What are the factors responsible for radioactivity in
some nuclides and not in others?
A plot of the number of neutrons versus the
number of protons in stable nuclei will provide
an answer
• The solid line shows where nuclei with an equal
number of neutrons and protons would fall. Along
this line Z = N i.e. neutron / proton ratio = 1:1
• Isotopes of lighter elements up to 40/20Ca fall on
or quite close to the n=p line, while heavier
elements n increases faster than p and the n/p
ratio eventually reaches about 5:3
24
26
 BAND OF STABILITY (NEUTRON/PROTON RATIO)
• The additional neutrons provide the additional
nuclear force necessary to hold larger no of
protons close together within the nucleus
• Once At. No. reaches 83, even extra neutrons
cannot maintain stability
• Hence, all known nuclides of Z > 83 are unstable
and radioactive
• For each nuclear charge, only isotopes with a
neutron – proton ratio within a specific range
(band of stability) are stable and not radioactive
27
 BAND OF STABILITY (NEUTRON/PROTON RATIO)
• Essentially, radioactivity is the spontaneous
transformation of unstable nuclei to nuclei with
more favorable n / p ratios
• Nuclides with too many protons fall below the
stability band and decay so that there is a
decrease in the number of protons relative to the
number of neutrons (greater n / p ratio)
• Nuclides with too many neutrons are above the
stability band and decay so that there is a
decrease in the number of neutrons relative to
the number of protons (smaller n / p ratio)

28
 BAND OF STABILITY (NEUTRON/PROTON RATIO)

• Thus, the elements are beta emitters, since

beta decay has the overall effect of losing a
neutron and gaining a proton:
1 n  1 p + 0 e
0 1 -1
for example 209F  2010Ne + 0-1e
beta decay of fluorine – 20 reduces the n / p
ratio from 11 / 9 to 10 / 10 thereby moving the
surviving nucleus (Neon – 20) closer to the
center of the stability band.

30
 BAND OF STABILITY (NEUTRON/PROTON RATIO)
• However, positron emission has the opposite
effect (increasing n / p ratio) e.g. fluorine – 17
improves its stability by emitting a positron:
17 F
9  17 O +
8
0 e
+1
(n / p = 8 / 9 to 9 / 8)
• Positron decay by Mg – 23 to Na – 23 produces a
similar favorable shift
• The heavy nuclei above atomic number 83 are
alpha emitters, because their nuclei have too
many protons for stability. The loss of an alpha
particle is the quickest way to get rid of protons

31
 Odd – Even Rule
• When the numbers of neutrons and protons in
a nucleus are both even, the isotope is far
more likely to be stable than when both
numbers are odd
• Out of the 264 stable isotopes, only five have
odd numbers of both protons and neutrons,
whereas 157 have even numbers of both
• The rest have an odd number of one nucleon
and even number of the other
• 21H, 63Li, 105B, 147N and 13857La have odd no of
protons & neutrons
32
 Odd – Even Rule
• related to the spins of nucleons, both protons
and neutrons have spins like orbital electrons
• When two like particles have paired spin (i.e.
opposite spins), their combined energy is less
than when their spins are not paired
• Therefore, when there are even numbers of
protons and neutrons, all spins can be paired and
the system has less energy (and is more stable)
than when an odd proton or neutron is present
• The least stable nuclei tend to be those with both
odd nucleons

33
 Magic Numbers
• another rule on nuclear stability based on the
magic numbers of nucleons.
• Isotopes with specific numbers of protons or
neutrons (magic numbers) are more stable than
the rest
• magic numbers are 2, 8, 20, 28, 50, 82 & 126
• When both nucleons are the same magic number,
the isotope can be quite stable e.g. 42He, 168O and
40 Ca
20
• one stable isotope of lead 20882Pb has 82 protons
and 126 neutrons, both magic numbers
34
 Magic Numbers
• magic numbers existence supports the
hypothesis that there are nuclear energy
levels just as there are electron energy levels
• Electron orbitals have a set of magic numbers
of their own – the maximum number of
electrons that can be in a principal energy
level
• These are 2, 8, 18, 32, 50, 72 and 98 for
principal levels 1 – 7 respectively

35
 Transmutation
• With the capture of a high – speed particle by a
nucleus, the nucleus can be permanently
changed to that of another element
• This change from one isotope to another is called
transmutation
– radioactive decay is one way that makes this
possible
– can also occur by bombarding the atoms of an
isotope with high energy particles
alpha particles from natural alpha emitters
neutrons from atomic reactors
protons made by the removal of electrons from
hydrogen
36
 Transmutation
• With electrically charged nature of alpha
particles & protons they can be accelerated to
ultrahigh energies in special accelerators
• With sufficient energy, bombarding particles
can shoot through the electron orbitals & bury
themselves in nuclei
• Beta particles (electrons) are strongly repelled
by the orbital electrons
– are therefore unable to get through in most cases
& are not used to cause transmutations
37
 Formation and decay of Compound** nuclei
• With capture of bombarding particle, compound
nucleus is formed which has all of the energy of
the bombarding particle & is therefore unstable
• Its additional energy is soon distributed among all
of its nuclear particles but eventually the nucleus
has to get rid of the excess energy
– by ejecting a high – energy particle such as
a neutron
a proton
an electron
by emitting gamma radiation
• The overall effect is a transmutation
38
 Transmutation
The first transmutation to occur under laboratory
conditions was by Rutherford
4 He + 14 N  18 F**  17 O + 1 p
2 7 9 8 1
(178O is a rare but stable isotope)
{** = high energy}
• Alpha particles and protons pick up speed and
energy when they are attracted towards a
negatively charged object
– These led to the development of a number of particle
accelerators – gigantic machines such as cyclotrons

39
 Transmutation
The first experimentally induced transmutation
was the conversion of lithium – 7 to helium – 4

• The target captured a proton to give a

compound beryllium nucleus, which promptly
breaks into two alpha particles:-

3Li  
1 7 8 2 42He
1p + 4Be**

40
 Transmutation
• decay pattern depends on the amount of
energy, not on the bombarding particle used
in producing it e.g.
high – energy aluminium – 27 compound
nucleus could be made
• using alpha particles, protons or deuterons:
42He + 2311Na  2713Al**
11p + 2612Mg  2713Al**
21D + 2512Mg  2713Al**.

41
 Transmutation
• Once formed, the high-energy compound
nucleus has the following decay modes,
depending on the amount of energy it has
27
13 Al**  27 Al + 0 
13 0
27 Al**  26 Mg + 1 p
13 12 1
27 Al**  26 Al + 1 n
13 13 0
27 Al**  25 Mg + 1 n + 1 p
13 12 0 1
27 Al**  23 Na + 4 He.
13 11 2

• All isotopes are stable except Aluminium – 26

with a half – life of 7.4 x 105 yr
42
 Radionuclides above number 83
• From the standpoint of practical applications,
most useful transmutations produced
radionuclides with sufficiently long half – lives
for use in research, medicine & technology
• Over 1000 radionuclides have been made by
transmutations and many are isotopes that do
not occur in nature
• Many naturally occurring isotopes exist above
83 but all have long half lives

43
 Radionuclides above number 83
• Many of the other possible isotopes above 83
may well have existed at one time in nature,
but had half – lives too short in relation to the
age of the planet to have survived into the
20th century
For example, neptunium – 237, with a half life of over 2
million years, undoubtedly existed naturally at one time
• estimated age of the earth is over 4 billion years,
long enough for all the neptunium to have decayed
 Neptunium – 237 is known today because it can be
made in accelerators.
44
 Radionuclides above number 83
• None of the known elements from 93
(neptunium) and above, the transuranium
elements, occurs naturally
• They have all been made using high energy
bombardment techniques in nuclear reactors and
accelerators
• The synthetic elements 93 – 103 complete the
actinide series of the periodic table
• Elements 104, 105, 106, 107 & 109 have been
made but are surrounded by controversies which
have complicated naming them

45
 Radionuclides above number 83
• To make heavier elements, bombarding
particles that are larger than neutrons have
been used
alpha particles
highly accelerated cations from isotopes like
carbon -12
nitrogen -15
oxygen -18 &
neon - 22

46
 Condensed Nuclear Equations
• equations for some transmutations used in
synthesizing new heavy elements are
complicated by multiple processes
To simplify, scientists use condensed forms; this
has the bombarding and product particle written
in bracket between the symbols for the reactant
and product nuclides
23892U + 10n = 23993Np + 0-1e
23892U (n, e-) 23993Np
23892U (n, β-) 23993Np

47
 Condensed Nuclear Equations
• Exercise I: Many neutrons, alpha and other
particles are produced in reactions between
cosmic rays and nuclei near the top of the
earth’s atmosphere. Most of the neutrons
produced then react with 14N to produce 14C
as indicated by the shorthand equation: 14N
(n, p) 14C. Write the nuclear equation for this
reaction

48
 Condensed Nuclear Equations
• Solution: bombarding particle is a neutron
while the product particle is a proton.
Complete equation is
14 N + 1 n = 14 C + 1 H
7 0 6 1
• Exercise II: Write the shorthand notation for
the equation
242 Cm + 4 He = 245 Cf + 1 n
96 2 98 0
• Answer: 242Cm (α, n) 245Cf

49
 Detection devices
• detection and measurement of radiations are
possible since they are able to generate ions in
matter
• All radiations described so far are ionizing
radiations. When ions are produced in a gas,
even momentarily, the gas becomes a
conductor of electricity
• Geiger – Muller tube is based on this fact & is
particularly useful in detecting beta and
gamma radiations
50
 Geiger – Muller tube
• When a pulse of radiation enters the thin-walled
window of the tube
• ions are created in the gas inside, which allows a
pulse of electricity to flow from the cathode
(metallicized surface of the tube) to the anode (a
wire electrode)
• This flow of current activates an instrument that
amplifies the current and records the pulse
• The tube and the associated equipment is called
a Geiger counter

51
 Cloud Chambers
• for visualizing the actual tracks of particles of
radiation, several kinds of cloud chambers have
been invented
• When an enclosed space is briefly made
supersaturated in the vapor of some fluid (water
or alcohol) while it is exposed to radiation,
microdroplets of condenced vapor form along
any path taken by a particle
• The existence of some fundamental atomic
particles was initially inferred by analyses of
photographed tracks produced by cloud
chambers

53
 Scintillation Counters
• devices which permit an investigator to see when
a collision occurs between a particle and a special
surface on the counter
This surface is coated with a substance that gives off a
tiny flash when it is hit by a particle of radiation
a coating containing zinc sulphide phosphor allows
alpha particles to produce visible scintillations
can be magnified with electronic equipment and
automatically counted.
• Energy received from radiations striking the
phosphor at the top of this probe is processed by
the photomultiplier and sent to the amplifier
before counting

54
 Dosimeter
• used to measure the total quantity of radiation
received by a surface during a specific interval of time
• Some use photographic plates that are kept completely
shielded from ordinary light but that are sensitive to
atomic radiations including gamma and X – rays
 The amount of darkening in the developed film is
proportional to the dose of radiation received and can
therefore be measured
• Photographic films are also used to record X – rays in
medicine
 Dense tissues like bones, reduce the intensity of X – or
gamma rays
 Therefore if the radiation passes through the body toward a
photographic plate, shadows of bones will be cast on the plate &
will show up as a familiar “X – ray” picture

55
 Units of Radiation
• When the radiation department of a hospital
buys a radioactive material, it is particularly
interested in the activity of the sample
• Activity refers to the number of nuclear
disintegrations per second occurring in the
sample

56
 The Curie and the Becquerel
• Becquerel (Bq)is the SI unit of activity equal to one
disintegration or other kind of nuclear transformation
per second {named after Henri Becquerel (1852 –
1908), who discovered radioactivity and won a Nobel
prize in 1903}
• An older, pre SI unit of activity, which is still widely
used was named after Marie Curie (the discoverer of
radium). One Curie, Ci, equals the rate of
disintegration that occur in a sample of 1.0 g of
radium, which is 37 billion disintegration per second.
1 Ci = 3.7 X 1010 disintegration/s = 3.7 X 1010 Bq
If a hospital owns a radioactive source rated as 1.5 Ci,
the source delivers 1.5 X 3.7 X 1010 = 5.6 X 1010 Bq. 57
 The Rad and the Gray
• Rad = radiation absorbed dose
• the Gray is named after Harold Gray, a British
radiologist
These units are used to describe the quantity or dose of
radiation absorbed by some material
The most common in the US is the rad (rd), 1 rd
corresponds to the absorption of 10-5 J per gram of
tissue
The SI unit of absorbed dose is called the gray (Gy), 1 Gy
correspond to 1 joule of energy absorbed per kilogram
of absorbing material.
1 rd = 10-5 J per gram.
1 Gy = 1 J per kilogram
Therefore, 1 Gy = 100 rd 58
 The Rem (radiation equivalent for man)
• setback of the rad is that radiation damage is a
function not just of the absorbed energy but also
of the kind of radiation
• Neutrons are more dangerous than beta
radiations of the same energy and intensity
• “rem” was devised to account for the differences
• The dose in rad is multiplied by a conversion
factor that reflects the effectiveness of the kind
of radiation in causing damage, to give the dose
in rem

59
 The Rem (radiation equivalent for man)
• Conversion factor for alpha radiation is 20 X
rad dose, neutron radiation = 2 – 10 X rad
dose
• However, the rem dose is numerically about
the same as the rad dose for beta and gamma
radiations and X-rays
One advantage here is that doses are additive,
unlike the rads

60
 Radiation and Matter
• decay of radioactive nuclide
– mass lost & energy released
– energy given up mainly as the KE (particles &
nuclei)
– collide with surrounding atoms & molecules
gradually losing energy
– The effect depends on several factors like
state & type of matter, energy of radiations,
and type of radiation

61
 Radiation and Matter
• decay of radioactive nuclide
– Valence electrons may be knocked out, to
produce ions or pushed up to excited states,
then X – rays emitted ground state
– Highly reactive atoms or molecules with
unpaired electrons may be produced
– In some cases, anions are formed or chemical
bonds are broken

62
 Radiation and Matter
• Ionizing radiations from radioactive sources
– Electromagnetic radiation (X-rays & γ-rays)
– Particle radiation (α-rays, β-rays, neutrons etc)
• Distance travelled depends on medium & type
– highly penetrating γ-rays, neutrons are even more so
– Al 5 – 11 cm thick required to stop γ-rays which can
penetrate deeply into the human body or even pass
through it
– β-rays are considerably less penetrating than γ-rays
– travel several meters but penetrate only few mm into
human tissue
– α-Rays, least penetrating, traveling only few cm in air
& stopped by a sheet of paper or a layer of clothing. 63
 Radiation and Matter
• When radiations originate outside the body
– γ- & neutron radiations most hazardous
– body easily shielded from α and β particles
• Neutron radiation very damaging
– collide with nuclei cause recoil of nuclei that break
bonds
– lower energy give radionuclides that decay further
• α particles become more dangerous
– When radioactive material is created in the body
– enters the body through a wound
– by being inhaled or swallowed
– Internally, give up all their energy to the tissue in a
very small distance, causing great damage
64
 Background radiation
• Everyone is exposed to radiation
– People living in high elevations or travelers in jet
planes are more exposed to cosmic rays than
those who live at sea level
– Uranium & its decay products present in natural
building materials
• living in a stone or brick house increases radiation
exposure compared with living in a wooden house.
• Smoking a packet of cigarettes a day yields
40m rem/yr of radiation from radioactive
isotopes that concentrates in tobacco leaves
65
 Background radiation
• Potassium, an essential element for plants
small amounts of potassium – 40 is taken with
all food
• Carbon – 14 also present in all the food that we
eat
• Human body has about 5 X 105 nuclear
disintegrations occurring every minute
• Additional exposures
– X – rays used for diagnosis or therapy
– pollutants released by nuclear power plants or
present in smoke from coal – burning power plants

66
 Effect of Radiation
• Radiation damage severity is dependent on
many factors & varies from individual to
individual
• Irradiated organism or plant may undergo
– somatic effects
• changes in cell structure, immediate or delayed, that
may be damaging but will not be passed to future
generations
– genetic effects
• changes in genes that will produce physical changes in
future generations

67
 Effect of Radiation
• Intense short – term exposure to radiation,
leads to immediate somatic damage
– 25 rem exposure, raises white blood cell count
which returns to normal in a few months
– 200 rem exposure, induces nausea & fatigue and
reduces infection – fighting capability
• can cause death in about six weeks
– 400 rem, fatal to 50% of those exposed, causes
damage to bone marrow & spleen

68
 Effect of Radiation
• Radionuclides incorporated into the body cause
damage by exposure over a long time span
– cancer may be initiated by
• radioactive iodine that concentrates in the thyroid glands
• radioactive calcium, strontium and radium that concentrates
in bones.
• Long time exposure to low level background
radiation can lead to
– mutations – changes in the structure of the DNA
molecule that carries the code of heredity
– difficult to estimate the percentage of mutation that is
caused by background radiation since there are other
natural causes of such mutations

69
 Radiation Protection
• Impossible to avoid background radiation, need to
minimize exposures from other sources
– use radiation shielding materials
– staying as far as possible from radiation source
• Gamma radiations & X – rays
– effectively shielded only by dense materials such as lead
– Low density materials like cardboards, plastic or aluminium
are poor shielders
– Thick concrete is good & relatively cheap material
• Staying as far as possible
– effective in providing radiation protection
• intensity of radiation diminishes with the square of the distance
from the source.

70
 Radiation Protection
• Doubling one’s distance from the source
reduces the intensity by a quarter
– relationship between the distance and intensity
(inverse square law) – radiation intensity 1/d2 where d
is the distance from the source
• If the intensity I1 is known at distance d1, then
intensity I2 can be calculated using the
following equation
I1 / I 2 = d22 / d12
 law applies only to a small source that radiates
equally in all directions & with no intervening
shields.
71
 Radiation Protection
Doubling one’s distance from the source reduces
the intensity by a quarter
• Example: at 1.5m from a small
radioactive source, the radiation intensity
was 40 units. If the operator moves to a
point 4.5m from the source, what is the
radiation intensity?
• Solution: 40 / I2 = (4.5)2 / (1.5)2
I2 = 4.4 units
72
 Radiation Protection
• Exercise: If an operator is exposed to 1.4 units of
radiation at 10m from the radiation source, what will
be the intensity of radiation if he moves to 1.2m from
the source?

APPLICATIONS OF RADIOACTIVITY
• Chemical properties of radionuclides are the same as
those of the stable isotopes of the same element
– ordinary physical properties
• solubility
• dialysis
– exploited in several practical applications of radioactivity
for medical or analytical purpose

73
 APPLICATIONS OF RADIOACTIVITY
• Tracer Analysis
• Neutron Activation Analysis
• Isotope Dilution Analysis
• Radiological Dating
• Medical Uses
• Agricultural Uses

74
 Tracer Analysis
• Radionuclide location signaled by it’s radiations
– If moved elsewhere by chemical & physical properties,
position can easily be found
• Tracer analysis also used to pinpoint the locations
of brain tumours
– which uniquely concentrate pertechnitate ion, TcO4-,
made from technetium 99m*. (* = metastable form –
higher energy)
• Biochemists find out how plants or animals use
simple molecules to make more complex ones
– Plant’s roots allowed to dip for some time into a
solution containing bicarbonate ion made with carbon
– 14 (t1/2 = 5730yrs, β emitter).
75
 Tracer Analysis
• Whether ion is used to make organic compounds,
can be determined when the plant is harvested
and separated into the compounds of interest
– easy to detect any compound containing extra carbon – 14
• Compound further analyzed to find out which of
it’s molecular locations that normally have
carbon atoms are made of C – 14, instead of C –
12
• Information used to construct theories of
biochemical pathways in the synthesis of complex
molecules
76
 Tracer Analysis
• Similarly, fate of iodine in the human body can be
determined
– by having an individual drink a solution of dissolved
iodides containing a small quantity of radioactive
iodine as a tracer
Abnormality in the thyroid gland can be detected
• Industrial applications are numerous
– fate of catalyst in chemical plant followed by
incorporating a radioactive tracer in the catalyst
• 192Ir in a Pt – Ir catalyst
• Activity of 192Ir  rate at which the catalyst is moving & to
which part of the chemical plant, determined
77
 Neutron Activation Analysis
• Technique used for analyzing concentration of
an element in a substance
– based on the fact that a number of stable nuclei
can be changed into gamma emitters by capturing
neutrons
M 1 n (M + 1) * → (M + 1) 0 γ
AX + 0 → A X AX + 0
(M = mass no, X = isotope, A = atomic no)
• Each kind of neutron enriched nucleus emits
gamma radiation at its own frequencies,
which are known
78
 Neutron Activation Analysis
• By measuring gamma radiation intensity,
concentration of the element can be determined
• Technique so sensitive, concentrations as low as
10-9 % can be detected
• Museum with lock of hair of a famous person who
died long ago. Historian suspects murder by arsenic
poisoning
• If suspicion is true, some arsenic would be present in
the hair
– neutron activation analysis can detect it without
destroying the lock of hair

79
 Isotope Dilution Analysis
• Concentration of some component in a
mixture or the volume of a fluid that is
difficult to measure, can be determined
–manufacturer of vitamin B – 12, using a
fermentation system might want to know how well
a particular batch is progressing
–Usually, such mixture is very complex &
concentration of the vitamin is low in most
circumstances
–Isotope dilution analysis is used to detect the
concentration

80
 Isotope Dilution Analysis
• Vitamin B – 12, coordination compound with
cobalt as the central ion
• Vitamin prepared with cobalt – 60, a gamma
emitter (B – 12*)
• Known mass of the previously prepared B –
12* with a known specific activity (curies or
becquerels per unit mass) stirred into a
sample of the fermentation batch

81
 Isotope Dilution Analysis
• Then B -12* fully mingles with the B – 12
already synthesized by the medium
• Measured but small amount of the batch then
withdrawn & its vitamin B – 12 (B-12 + B-12*)
extracted and purified until it has a constant
specific activity
• Extent of dilution of the original B-12* can be
used to calculate the amount of B-12 in the
batch

82
 Isotope Dilution Analysis
Initially, a = m X So (in µCi)
(m + n) = (B-12 + B-12*)
a = (m + n) X S
Since total activity, a, does not change
but is only diluted

Therefore m X So = (m + n) X S

Amount of B-12 originally present, n = m(So/S -1)

83
 Isotope Dilution Analysis
Example: A vit-B complex tablet with a mass 4.77mg
was dissolved in water, then 0.407mg of radioactive
vit B-12 with specific activity of 2.406 µCi/mg was
added. After thorough mixing, the sample isolated
had specific activity of 1.490 µCi/mg. Calculate the
concentration of vit B-12 in the tablet in µg of B-12
per mg of B complex.
Solution: n = 0.407 X (2.460/1.490 -1)
= 0.407 X 0.651 = 0.265 mg
= 265 µg
265 µg/4.77 mg = 55.6 µg/mg
84
 Radiological Dating
• Determination of age of geological deposit or
archaeological find
– Radionuclides and their half-lives
• Wooden objects – Carbon 14 analysis
– Compares ratio of C-14 to stable C in ancient
sample with one recently produced
– Half-life of C-14 = 5730 years
– Current specific activity = 918 Bq / g of Carbon

85
 Radiological Dating
If bone from tomb had specific activity of 459
Bq/g of C, the bone has been dead for one
half-life period i.e. 5730 years
Nt ʎt
Log /No = - /2.303
0.693 0.693
t1
/2 = /k i.e. 5730 = /k
-4
Therefore k = 1.21 x 10 yr-1

86
 Radiological Dating
Example: What %age of 6831Ga sample which has
t1/2 of 68.3 min would remain at the end of 3
hrs?
0.693
Solution: rate constant for decay k = / 68.3
= 0.0101 min-1
Nt ʎt
Log /No = - /2.303 = - (0.0101)(180)/2.303 = -0.789
Nt
Fraction of isotope remaining = /No
Nt Nt
Log /No = -0.789 hence /No = 0.163
%age remaining = 16.3%

87
 Radiological Dating
• 14C
for dating objects less than 50,000 yrs old
• 40 K  40Ar & 238U  208Pb dating older
objects (t1/2 = 1.3 & 4.5 billion years, resp.)
• 40 K  40Ar can date up to 1 million yrs old
Gaseous Ar easily lost. K/Ar not as reliable
• Latter based on natural 23892U decay series 
206Pb (all assumed from U in the mineral)

 Meteorite that was 4.6 billion yrs old fell in Mexico in 1969.
Results of U/Pb studies indicated that our solar system was
formed several billon yrs ago
88
 Medical Uses of Radionuclides
• 60 Co
27  6028Ni + 0-1β + 00γ
γ rays to destroy cancerous tissues
• Radioisotopes used to label elements in
compounds, monitored throughout the body
e.g. 24Na injected into blood stream to
monitor blood flow and locate obstructions
• 201Tl concentrates in healthy heart tissue
(thallium) whereas 99Tc (technetium)
concentrates in abnormal heart tissue.
Hence both can be used to survey damage
from heart disease
89
 Medical Uses of Radionuclides
• 131Iconcentrates in thyroid gland, liver &
certain parts of the brain
– monitor goiter & other thyroid problems
– Liver & brain tumours
• Energy from Plutonium – 238 decay
converted into electrical energy in heart
pacemakers
– Used for 10 years b/4 replacement

90
 Agricultural Uses of Radionuclides
1. DDT (pesticide) toxic on repeated exposure.
γ-ray irradiation of male screw-worm flies,
sterilizes & subsequent release in infested
area results in NO OFFSPRING (females mate only
once)  entire population wiped out
2. γ-irradiation of some foods  longer period
of storage e.g. retardation of sprouting in
potatoes & onions

91
 TRANSITION ELEMENTS
A transition metal is one which forms one or
more stable ions which have incompletely filled
d orbitals
o scandium & zinc don't count as transition metals -
even though they are members of the d block
Sc3+ ion has no d electrons (electronic [Ar] 3d14s2)
Zinc ion has full d levels (electronic [Ar] 3d104s2)
 By contrast, copper ([Ar] 3d104s1 ) forms two ions -
Cu+ ([Ar] 3d10) & more common Cu2+ ([Ar] 3d9)
 TRANSITION ELEMENTS
• Elements in the middle of the periodic table (d-
block)
• transition between
– “base formers” on the left (Gp I & II)
– “acid formers” on the right (Gp III  VIII)
• term applies to both d- & f- transition elements
• They are all metals, hence “transition metals”
• The f-transition elements rare earths or inner
transition elements
TRANSITION ELEMENTS – 1ST ROW
 GENERAL PROPERTIES
• MUST have a partially filled set of d orbitals,
either as a metal or compound
• Zn, Cd, Hg & their cations have completely
filled d orbitals not really d-transition
elements
• All other elements have partially filled d
orbitals except IB elements & Palladium
• Some cations of latter elements have partially
filled sets of d orbitals
 GENERAL PROPERTIES
• All are metals
• Most are harder & more brittle, and have higher
mp, bp and heats of vapourization than
nontransition metals
• Ions & compounds are usually coloured
• form many complex ions
• Exhibit multiple oxidation state, except a few
• Many are paramagnetic, just like their
compounds
• Many of the metals and their compounds are
effective catalysts
 Electron configuration

• Sc [Ar] 3d14s2 • Fe [Ar] 3d64s2

• Ti [Ar] 3d24s2 • Co [Ar] 3d74s2
• V [Ar] 3d34s2 • Ni [Ar] 3d84s2
• Cr [Ar] 3d54s1 • Cu [Ar] 3d104s1
• Mn [Ar] 3d54s2 • Zn [Ar] 3d104s2
Electron configuration and Oxidation State
• Addnal stability associated with half- or fully-
filled orbitals responsible for 24Cr & 29Cu
• Properties can be correlated with either no of
d e- or no of unpaired e-
• Most exhibit more than one O. State
– Max O. S. is given by metal’s group no, which may
not be the most stable oxidation state
• Most common are +2, +3 & +4, with +5 & +6
next
Electron configuration and Oxidation State
IIIA IVA VA VIA VIIA VIII IB IIB
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2r +1r +1r +1r +1r +1r +1r
+3 +3r +2r +2r +2 +2r +2 +2 +2 +2
+4 +3r +3 +3o +3 +3o +3o +3o
+4 +4o +4o +4o +4o +4o
+5o +5o +5o +5o
+6o +6o +6o
+7o
Electron configuration and Oxidation State
• Elements in the middle (each series) exhibit more OS
• Down the group, higher OS more stable & common
(cf maingroup elements)
– More effective shielding from nuclear charge
– Easily ionized
– More readily available for sharing
 Co = +2 & +3
 Rh & Ir (below Co) exhibit +3 and +4 oxidation states
 +4 slightly more stable for Ir than for lighter Rh
 Classification into Sub-groups
• Subdivided into 8 groups – I  VIII
• Elements form many compounds of similar
stoichiometry (though dissimilar chemical properties)
I II III IV V VI VII
NaCl MgBr2 Sc(NO3)3 TiCl4 VOCl3 CrO42- Mn2 O7
KNO3 CaCl2 Y(OH)3 ZrO2 VO43- H2Cr2O 7 HMnO4
CuCl ZnBr2 Al(NO3)3 CCl4 POCl3 SO42- Cl2 O7
AgNO3 CdCl2 Ga(OH)3 PbO2 PO43- H2S2O 7 HClO4
 Classification into Sub-groups
• VIII consists of 3 gps of metals  3 horizontal
triads
– Fe  Fe Co & Ni
– Pd  Ru Rh & Pd
– Pt  Os Ir & Pt
• Some trends are common to both sub-groups
– Corresponding compds in same OS, covalent
character decreases & ionic character increases
down the group
 Classification into Sub-groups
• Some trends are common to both sub-groups
– Increasing electrical conductivity in aq solns &
increasing mps/bps for the heavier compounds
V2O 5 - 690° Nb2O 5 - 1460° Ta2O 5 - 1800°
melting point {indicates increasing ionic
character}
– Compounds in diff proportions, lower OS usually
more ionic
• TiCl2 & TiCl3 are ionic solids whereas TiCl4 is
molecular liquid
– For given TE, O2- & OH- of lower OS are basic,
intermediate  amphoteric and high OS  acidic
 Colour
• Most are coloured (distinctive characteristic)
• Splitting of d orbitals  t2g & eg ; separated by
energies ~ wavelength of visible light
• Absorption of light causes electronic
transitions b/w these orbitals
• White light (ROYGBIV) – substance absorbs
light of particular wavelength
– Absorbs orange and appears BLUE
• Complementary colour = light not absorbed
and seen
 Colour
Wavelength Spectral Complementary
4100 Violet lemon yellow
4300 Indigo yellow
4800 Blue orange
5000 blue-green red
5300 Green purple
5600 lemon-yellow violet
5800 Yellow indigo
6100 Orange blue
6800 Red blue-green
 Colour
• t2g  eg depends on ligand;
• frequency / wavelength / colour absorbed related to
Ʌo
– Depends on crystal field strength of the ligands (ability to
split d orbital)

• Colour / visible absorption spectra of transition metal

complexes (as well as magnetic properties)

– Give info about the strengths of the ligand – metal

interactions
approximate colours for some common transition metal
complex ions
 Atomic Radii
• Decreases from left to right – increase in
nuclear charge
• Increases near end of series – increase in
effective nuclear charge outweighed by
greater repulsions (d e- in nearly filled
orbitals)
• Increases down the group but 3rd row TS
have nearly same as 2nd row TS due to
LANTHANIDE CONTRACTION???
 Atomic Radii
• LANTHANUM (La – 57)

• f electrons less shielding than d < p < s

• Higher effective nuclear charge is felt by
outermost electron
–Smaller radii than expected
 Magnetism
• Unpaired e-  paramagnetism (attracted to)
• Absence  diamagnetism (repelled by)
• Paramagnetism
– Electron spinning on its axis  magnetic moment
– Clockwise & anticlockwise = diamagnetic
– Electron movement in elliptical orbit  moment
µs = 1.73, 2.83, 3.87, 4.90, 5.92 BM
for n = 1, 2, 3, 4 & 5 unpaired
electrons respectively
 Magnetism
• Magnetically dilute – paramagnetic centers
separated by diamagnetic ligands {prevents
interactions b/w centers}
• Ferromagnetism – much stronger than
paramagnetism
– Unpaired e spins align themselves to give
impression that there are more electrons
• Antiferromagnetism
– Unpaired e spins align themselves to give
impression that there are less unpaired electrons
 diamagnetism (low spin complexes)
 The formation of complex ions
The molecules or ions surrounding the central metal ion
are called ligands e.g. water, ammonia and chloride ions

Some examples of complex ions formed by transition

metals
• [Fe(H2O)6]2+
• [Co(NH3)6]2+
• [Cr(OH)6]3-
• [CuCl4]2-
Coordination Compounds – “Complexes”
• Lewis base (ligand) attached to Lewis acid
(acceptor) by “lone-pair” of electrons
• Atom directly attached called ‘donor atom’
• Bonding varies from purely electrostatic (σ) to
multiple (both σ-donor & π-acceptor, with
metal in OS of +1 or less)
OS = valency
CN = no directly attached
“Complexes” = CN always > OS
Coordination Compounds – “Complexes”
• Most transition metals have vacant d-orbitals
 accept electron pairs
– Forming coordinate covalent bonds in
coordination compounds
Cationic
[Cr(H2O)6]3+ , [Co(NH3)6]3+ , [Ag(NH3)2]+
Neutral
[Fe(CO)5] , [PtCl2(NH3)2]
Anionic
[Ni(CN)4]2- , [Fe(CN)6]3-
Coordination Compounds – “Complexes”
• Many are very stable – low dissociation consts
• Include important biological substances
– Haemoglobin & Chlorophyll
• O2 carrying protein, contains Fe2+ bound to
large porphyrin rings
– Transport involves coordination & subsequent
release of O2
• Necessary for photosynthesis, contains Mg2+
bound to large porphyrin rings
• Vit. B-12 is a large complex of Cobalt
Coordination Compounds – “Complexes”
• Many practical applications
– Water treatment
– Soil and plant treatment
– Protection of metal surfaces
– Analysis of trace amounts of metals
– Electroplating
– Textile dyeing
 Manganese oxides & hydroxides
• Variation in chemical properties as Oxidation
State increases is typical of many T Metals
• +2, +3, +4, +6 & +7 in its simple compounds
• +2 state is most stable
• KMnO4 (+7), stable, very strong oxidizing
agent & common laboratory reagent
Acidity increases as OS increases
(A & B subgroups)
 Manganese oxides & hydroxides
Increasing covalent character; increasing acid strength 
+1 +2 +3 +4 +5 +6 +7
ClOH ClO(OH) ClO2(OH) ClO2(OH)
{HClO} {HClO2} {HClO3} {HClO4}
Hypochlorous chlorous chloric acid perchloric acid

Mn(OH)2 Mn(OH)3 MnO(OH)2 MnO2(OH)2 MnO3(OH)

{H2MnO3} {H2MnO4} {HMnO4}
manganous manganic permanganic
• Permanganic & perchloric acids – very strong acids & oxid. ag.
• Former exists only in soln but neutralized by bases – KMnO4
(very strong OA)
MnO4- + 8H+ + 5e-  Mn2+ + 4H2O E° = +1.51V
 Manganese oxides & hydroxides
• Manganous & manganic are also unstable
though salts can be isolated
• Mn (II) & Mn (III) are relatively stable
• Mn (II) air-oxidized to manganese
(II)oxyhydroxide MnO(OH)
Mn2O7 (dark brown explosive liquid) - HMnO4
anhydride
Cl2O7 (colourless explosive liquid) - HClO4
anhydride
 Manganese oxides & hydroxides
Properties in high OS are very much alike
Chemical properties are usually not as
similar for corresponding A & B group
elements
Mn = metal ; Cl = nonmetal
but trends in acidity & basicity as a
function of OS are similar
 Manganese oxides & hydroxides
• Other group VIIA elements form many compounds
with similar formulae (Mn)
• Heptoxides react with water  strongly acidic solns
Mn2O7 + 3H2O  2{H3O+ + MnO4-} permanganic
Tc2O7 + 3H2O  2{H3O+ + TcO4-} pertechnetic
Re2O7 + 3H2O  2{H3O+ + ReO4-} perrhenic
 Mn2O7 dangerously explosive
 Tc2O7 & Re2O7 are stable enough to be sublimed
 Evidence of increasing stability of higher O States as
transition metal group is decended
 GROUP IV ELEMENTS

C
Si
Ge
Sn
Pb
• Properties vary through this group.
• Tin and Lead are metallic
– +2 and +4 oxidation states
–  and  forms,  less stable < 13 C, tin pest or tin
disease.
• Germanium is metalloid.
• Silicon, though a semiconductor is mainly
nonmetallic.
• Carbon is a nonmetal.
 CARBON
• 12C isotope (predominantly)
• 13C (smaller amt)

• 14C (radioactive)

– archeological dating
– radioactive tracers
• 1st 4 Ionization Energies (much higher)
 CARBON
• Diamond (extremely unreactive @ rt)
• Graphite (layer structure) reacts more readily
– oxidized to mellitic acid C6(CO2H)6 {hot conc.
HNO3}
– active reducing agent
– reacts readily with many oxides
• liberate the element
• form carbide.
 CARBIDES
3 types which are similar
• Most polar (ionic) {electropositive metals}
• Most covalent (molecular) {electronegative
non – metals}
• Somewhat complex (interstitial) {elements in
the center of the d-block}
 Salt – like carbides
• Be2C and Al4C3 - sometimes called
“methanides”
– yield predominantly CH4 on hydrolysis
• C2 units are well known e.g. acetylides
(ethynides) of alkali metals MI2C2, alkaline
earth metals MIIC2 and the lanthanides LnC2
and Ln2C3 i.e. Ln4(C2)3
• Gp. IB (Cu, Ag, Au) are explosive
• Gp. IIB (Zn, Cd, Hg) are poorly characterized
 Salt – like carbides
• MI2C2 - colourless crystalline compounds
– react violently with water
– oxidized to carbonate on being heated in air
• CaC2 - most important compound
– production of ethyne (chemical industry & oxy -
acetylene welding)
– fixing N2 from air to give calcium cyanamide
{CaCN2}
• widely used as a fertilizer
 Interstitial Carbides
• Lanthanides form
– metal rich carbides M3C {normal carbides (LnC2)}
• Actinides form
– monocarbides MC (several early T. elements)
Which are infusible, extremely hard, refractory
materials that retain many characteristic
properties of metals
 Interstitial Carbides
• C atoms occupy octahedral interstices in a
closed-packed lattice of metal atoms
• Carbides of Cr, Mn, Fe, Co and Ni
– profuse in number
– complicated in structure
– great industrial importance e.g. cementite Fe3C
(important constituent of steel)
– Much more reactive than the interstitial carbides
of the earlier T.S.
 HYDRIDES AND HALIDES
• Catenation - best illustrated in the hydrides (organic
chemistry)
• Replacement of H by F as in CF4
– greatly increases both thermal stability & chemical
inertness
• great strength of the C-F bond
• Thus, fluorocarbons
– resistant to attack by acids, alkalis, o. agents, r. agents and
most chemicals up to 600 oC
– Immiscible with both water & hydrocarbon solvents
– when combined with other groups
• confer water-repellance and stain resistance
– paper, textiles & fabrics
 OXIDES
• Forms 2 extremely stable oxides - CO & CO2
• 3 oxides of considerably lower stability (C3O2,
C5O2 and C12O9)
• number of unstable or poorly characterized
oxides like C2O, C2O3
 OXIDES
• Tricarbon dioxide C3O2
– foul-smelling gas
– from dehydration of malonic acid @ reduced
pressure over P4O10 at 140oC
– polymerizes at rt to a yellow solid
O=C=C=C=O
– readily rehydrates to malonic acid, CH2(CO2H)2
– reacts with NH3&HCl to give amide & acid chloride
CH2(CONH2)2 and CH2(COCl)2
 CYANIDES
• Cyanogen (CN)2
– colourless poisonous gas (like HCN)
– possessing considerable thermal stability (800 oC)
when pure
– presence of trace impurities normally results in
polymerization at 300-500 oC to paracyanogen
with a condensed polycyclic structure
 SILICON

• 28Si (92%) with ~5% 29Si & 4% 30Si

• more volatile than C
– substantially lower energy of vaporization (smaller
Si - Si bond energy)
• Semiconductor
– distinct shiny, blue – grey metallic lustre
 SILICON
• Massive crystalline form
– relatively unreactive except at high t.
– Formation of very thin continuous, protective surface
layer of SiO2 makes rxn with O2, water and steam, less
effective
– Oxidation in air - not measurable below 900 oC
– between 950-1160 oC rate of formation of vitreous
SiO2 rapidly increases
– at 1400 oC, N2 in air gives SiN & Si3N4
– Sulphur vapour reacts at 600 oC
– P vapour reacts at 1000 oC
– unreactive towards aq. Acids
– conc. HNO3 / HF oxidizes & fluorinates the element
 SILICON
• Molten Si (in contrast)
– extremely reactive
• forms alloys or silicides with most metals
• rapidly reducing most metal oxides
– very large heat of formation of SiO2 (900 kJ mol-1)

• Silicon does not form binary compounds with

Ge, Sn, & Pb
• compound with C - SiC
– outstanding academic & practical interest
 SILICON CARBIDE
• Greater thermal stability than any other binary
compound of Si
– decomposition by loss of Si appreciable @ 2700 oC
• resists attack by most aq. acids (HF inclusive but
not H3PO4)
• oxidized in air only above 1000 oC {protective SiO2
layer}
– removed by molten hydroxides or carbonates thereby
accelerating oxidation.
• SiC + 2NaOH + 2O2 = Na2SiO3 + H2O + CO2
 SILICIDES
• All A-subgroup metals except Be
• greatest range Gps IVA – VIII (TMs) &Uranium
• No B-subgroup metals except Cu
• Gps. IA & IIA Silicides generally much more
reactive than those of transition elements
– Hydrogen and/or silanes are typical products
Na2Si + 3H2O  Na2SiO3 + 3H2
Mg2Si + 2H2SO4(aq)  2MgSO4 + SiH4
 SILICIDES
• Formulae cannot be rationalized by
application of simple valence rules
• Bonding varies
– essentially metallic to ionic & covalent
• Observed stoichiometries include
– M6Si, M5Si, M4Si, M15Si4
– M3Si, M5Si, M2Si, M5Si3
– M3Si2, MSi, M2Si3
– MSi2, MSi3, MSi6
 SILICON HYDRIDES (SILANES)
• Silanes, SinH2n+2
– known as unbranched & branched chains (upto n = 8)
– no cyclic compounds or unsaturated analogues of
alkenes and alkynes
– colourless gases or volatile liquids
– extremely reactive
• spontaneously igniting or exploding in air
– Thermal stability decreases with increasing chain
length
• only SiH4 is stable indefinitely at rt.
 SILICON HYDRIDES (SILANES)
• Much more reactive than the corresponding C
compounds
– (a) larger radius of Si which would facilitate
nucleophilic attack
– (b) great polarity of Si-X bonds
– (c) presence of low-lying d – obitals which permit
formation of 1:1 & 1:2 adducts
• thereby lowering the activation energy of the rxn
 SILICON HYDRIDES (SILANES)
• Pure silanes do not react with pure water or
dilute acids in silica vessels
• but even traces of alkali dissolved out of glass
apparatus catalyze the hydrolysis
– which is rapid and complete (SiO2.nH2O + 4H2)
• Solvolysis with MeOH can be controlled
– several products SiH4-n (OMe)n (n=2,3,4)
• Explodes in the presence of Cl2 or Br2
• rxn with Br2 can be moderated at –80o
– good yields of SiH3Br & SiH2Br2
 SILICON HALIDES
• Si & SiC react readily with all halogens
– colourless volatile reactive products SiX4
• Two different tetrahalides heated together
– they equilibrate to form a random distribution of
silicon halides
nSiX4 + (4-n)SiY4 = 4SiXnY4-n
• Higher homologues SinX2n+2
– volatile liquids or solids
• Catenation in Si compounds reaches its
maximum in the halides rather than the hydrides
(contrary to C)
 SILICON HALIDES
• Ascribed to additional back-bonding
– from filled halogen pπ obitals into the Si dπ
orbitals
• synergically compensation for electron loss from Si via
σ bonding to the electronegative halogens
• Fluoropolysilanes
• up to Si16F34
• up to at least Si6Cl14 and Si4Br10 are known
 SILICA
• Chemically resistant to all acids except HF
• Dissolves slowly in hot conc. alkali & more rapidly
in fused MOH or M2CO3
– M2SiO3
• Among halogens, only F2 attacks SiO2 readily
– SiF4 + O2
• Reaction of SiO2 with the oxides of metals &
semimetals
– great interest & importance in glass technology &
ceramics
 SILICATES
• Alkali metal carbonates fused with silica
(~1300o)
– CO2 + complex mixture of alkali silicates
• Basic unit of structure is SiO4 tetrahedron
– Occur singly or by sharing oxygen atoms, in small
groups, in small cyclic groups, in infinite chains or
in infinite sheets
• few simple discrete SiO44- orthosilicate anions
are known e.g. Be2SiO4
 SILICATES
• Simplest condensed silicate anion -
pyrosilicate ion Si2O76- formed by combining
two SiO4 tetrahedra with sharing of O atoms
e.g. Sc2Si2O7
• Cyclic silicates are known Si3O96- and Si6O1812-
e.g. BaTiSi3O9 and Be3Al2 Si6O18
• Infinite chain anions such as (SiO32-)n and
(Si4O116-)n are known.
 GERMANIUM, TIN AND LEAD
• Notable Pair wise similarities in I.Es
– Si & Ge (filling of 3d10 shell)
– Sn & Pb (4f14 shell)
• Ge
– brittle, grey –white lustrous crystals with diamond
structure
– metalloid with similar electrical resistivity to Si at rt
– mp, bp & associated enthalpy changes are also lower
than for Si
• Trend continues for Sn & Pb
– very soft, and low-melting metals
 CHEMICAL REACTIVITY AND TRENDS
• Ge
– more reactive and more electropositive than Si
– dissolves slowly in hot conc. H2SO4 & HNO3
– does not react with water or with dil. acids or alkalis
• unless an oxid. agent like H2O2 or NaOCl is present
– fused alkalis react to yield germanates
– oxidized in air at red heat GeO2
– H2S & S(g) yield GeS2
– Cl2 & Br2 yield GeX4 on moderate heating
– HCl gives both GeCl4 & GeHCl3
– Alkyl halides react with heated Ge (as with Si) to give
organogermanium halides
 CHEMICAL REACTIVITY AND TRENDS
• Sn
– notably more reactive & electropositive than Ge
• though still markedly amphoteric in its aq chemistry
– stable towards both water & air at ordinary temps
– reacts with steam to give SnO2 + H2
– heating in air or O2 gives SnO2
– Dil HCl and H2SO4 show little, if any, rxn
– dil HNO3 produces Sn(NO3)2 & NH4NO3
 CHEMICAL REACTIVITY AND TRENDS
• Sn
– Hot conc HCl yields SnCl2 + H2
– hot conc H2SO4 forms SnSO4 + SO2.
• Occurrence of SnII compounds in these rxns is notable
• By contrast, hot aq alkali yield hydroxostannate (iv)
compounds e.g
Sn + 2KOH + 4H2O K2[Sn(OH)6] + 2H2
• Reacts readily with Cl2 and Br2 in the cold, F2 & I2 on
warming to give SnX4
• reacts vigorously with heated S & Se, to form SnII & SnIV
chalogenides
– depending on the proportions used
• with Te gives SnTe.
 CHEMICAL REACTIVITY AND TRENDS
Finely divided Pb powder is pyrophoric
• reactivity is greatly diminished by formation of
a thin, coherent protective layer of insoluble
prd like oxide, oxocarbonate, sulphate or
chloride
• F2 reacts at rt to give PbF2
• Cl2 gives PbCl2 on heating
• Molten Pb reacts with the chalcogens to give
PbS, PbSe & PbTe
 CHEMICAL REACTIVITY AND TRENDS
• steady trend towards increasing stability of MII
rather than MIV compounds (Ge, Sn, Pb) - “inert
pair effect” {heavier B subgroup metals}
• Notable exception is the organometallic
chemistry of Sn & Pb which is almost entirely
confined to the MIV state
• Catenation is also impt for Ge, Sn, Pb chemistry
thought less so than for C & Si
• Ability of both Sn & Pb to form polyatomic cluster
anions of very low formal oxidation state (e.g
M52-, M94- etc)
– reflects the tendency of heavier B subgroup elements
to form chain, ring or cluster homo-polyatomic ions
 HYDRIDES AND HYDROHALIDES
• Germanes, GenH2n+2
– colorless gases or volatile liquids for n=1-5
– prepn , physical propts and chemical rxns very
similar to those of silanes
– though they are less volatile and noticeably less
reactive
– GeH4 does not ignite in contact with air (cf. SiH4 &
SnH4) & unaffected by aq acid or 30% aq NaOH
– acts as an acid in liq NH3 -> NH4+ + GeH3- ions
– alkali metals in liq NH3 -> MGeH3
 HYDRIDES AND HYDROHALIDES
Germanuim hydrohalides GeHxX4-x (X = Cl, Br, I;
x = 1,2,3)
• colourless, volatile, reactive liquids
– valuable synthetic intermediates (cf SiH3I) e.g.
hydrolysis of GeH3Cl yields O(GeH3)2
SnH4
• decomposes slowly to Sn + H2 at rt
• unattacked by dil aq acids or alkalis but
decomposed by more conc solns
• Potent reducing agent
 HYDRIDES AND HYDROHALIDES
• Sn2H6
– even less stable
• higher homologues not known
• By contrast, organotin halides are more stable
• catenation up to H(SnPh2)6H has been
achieved
PbH4
• least well characterized Gp IVB hydride
• unlikely that it has ever been prepd
 HALIDES
• Ge, Sn & Pb forms two series: MX2 & MX4
• PbX2 more stable than PbX4 whereas reverse is
true for Ge
• steady increase in stability thus:
CX2 << SiX2 < GeX2 < SnX2 < PbX2
• lighter members - colourless, volatile liquids
• GeI4 - orange solid (cf. CX4, SiX4)
• All hydrolyse readily
• GeCl4 - impt intermediate
– organogermanium compounds (LiR or RMgX)
 HALIDES
• SnX2 forms complex series
 presence of non-bonding e-s (5s2) result in
increase in coordination no.
– polymerization to rings or chains
– adduct [SnX2.(NMe3)] (X = Cl, Br, I)
– sometimes double adduct [BF3{SnX2(NMe3)}] (X =
Cl, Br, I) formation
• SnX4
– volatile liquids or solids comprising tetrahedral
molecules except
– SnF4 (unlike CF4, SiF4 & GeF4) is polymeric
• octahedral coordination about Sn
 HALIDES
• PbX2 - much more stable thermally & chemically
than PbX4
• PbF4 - only stable tetrahalide
• PbCl4 - stable below Oo ,but PbCl2 + Cl2 above 50o
• PbBr4 - even less stable
• PbI4 – doubtful
• PbX2 - stable crystalline compounds
– prepd from water soluble PbII salts & halide ions
or HX  ppt insoluble PbX2
 OXIDES
• GeO - reducing agent
– disproportionates rapidly to Ge + GeO2 above 700
o

• Impressive resemblance - oxide chemistry of

GeIV & SiIV
– Ge analogues of all the major types of silicates and
alumino-silicates have been prepd
• SnO oxidized to SnO2 (heated in air to 300o)
• disproportionates {GeO}(heated in absence of oxygen)
• mixed valence oxides e.g. Sn3O4 i.e. SnII2SnIVO4
 OXIDES
• SnO2(cassiterite)
– insoluble in water and dil acids or alkalis
– dissolves readily in fused alkali hydroxides
• “stannates” MI2 Sn(OH)6
• Conversely Hydrous tin (iv)oxide (white ppt)
– readily soluble in both acids and alkalis
• amphoteric nature of SnIV
 OXIDES
• PbO & mixed valence oxide Pb3O4
• PbO2 decomposes when heated

PbO2293oPb12O19351oPb12O17
374oPb3O4605oPbO
• Pb2O3
– obtained by decompn of PbO2 (or PbO) at 580-
620o under O2 pressure of 1.4 kbar.
 Uses of Carbon and its compounds
• Natural graphite
– Refratories, lubricants, foundaries, brake linings &
pencils
– Crucibles, retorts, stoppers, sleeves & nozzles
– Neutron moderator in nuclear reactors(ultra-high purity)
• Diamond
– Single point tools for engraving or cutting & for
surgical knives
– Bearings & wires dies
– Industrial abrasives for grinding & polishing
– Thermistors & radiation detectors
– Optical windows for lasers
 Uses of Carbon and its compounds
• Metallurgical coke is used for steel manufacture
(blast furnace)
• Carbon black is used for tyres, as pigments in
plastics, in printing inks & paints
• Activated carbon is used in the sugar industry as
decolourizing agent. Also in the purification of
chemicals & gases including air pollution & in water /
waste water treatment. In addition to catalytic uses
e.g. SO₂Cl₂ ← SO₂ + Cl₂
 Uses of Carbon and its compounds
• CO₂ solid used as refrigerant for ice-cream, meat
& frozen foods. Lab cooling agent & refrigerant.
• Liquid uses include rapid cooling of loaded trucks,
inflation of life rafts, fire extinguishers &
replacement of fluorocarbons in aerosols.
• Gaseous uses include carbonation of soft drinks,
purge gas, inert protective gas for welding &
neutralization of caustic / alkaline waste waters.
Manufacture of urea → urea formaldehyde
plastics & resins and as nitrogenous fertilizer.
 Silicon & its uses
• Ferrosilicon alloys
– Metallurgical industry to deoxidize steel
– Manufacture of high-Si corrosion resistant Fe
– Si/steel laminations for electric motors
• Semiconductor applications
– Transistors
• p – n acts as diode for rectifying alternating current
• n – p – n can act as a triode amplifier
• α-SiC
– electric heating elements
• β-SiC
– transistors, diode rectifiers, electroluminiscent diodes
 Industrial applications of silica
• α-quartz (piezoelectric material)
– Crystal oscilators & filters (frequency control & modulation)
– Electromechanical devices (transducers & pickups)
• Vitreous silica
– High quality lab glassware & sample cells for uv-vis
• Silica gel
– Desiccant, selective adsorbent, chromatographic support,
catalyst substrate and insulator (thermal & sound)
– Chemically inert/non toxic → anticaking agent in cocoa,
fruit juice powders, NaHCO₃ & powdered sugar/spices
– Matte finish on varnishes, paints & surface of vinyl
paints/synthetic fabrics
 Industrial applications of silica
• Fumed silica
– Thickening agent (processing epoxy & polyester
resins and plastics
– Reinforcing filler in silicon rubbers (non interference
with peroxide initiated cure)

• Diatomaceous earth
– Filteration plants
– Abrasives, fillers, light weight aggregates &
insulation material
– As inert carrier, coating agent
 Asbestos
• In reinforced cements
– Corrugated and flat roofing sheets
– Pressure pipes and ducts
– other hard-wearing, weather-proof, long-lasting products
• Asbestos papers and in manufacture of vinyl floor tiles
• Brake linings, clutch facing & other friction products
• Asbestos textiles
– Fire-fighting garments
– Numerous fire-proofing and insulating applications
• Asbestosis and lung carcinoma
– white not implicated but blue and brown type
 Tin and Lead Ores and Uses
• Cassiterite ore, SnO2, reduced with C to Sn.
• Galena, PbS, roasted in air then reduced with C.
• Alloys of Sn
– Solders
– Bronze (90% Cu, 10% Sn
– Pewter (85% Sn, 7% Cu, 6% Bi, 2% Sb)
• Pb
– Pimary use in storage batteries.
– Radiation shields.
 Oxides
• Lead
– PbO, litharge, yellow (ceramics, cements,
batteries).
– PbO2, red brown (matches, storage batteries).
– Pb3O4, mixed oxide known as red lead, red (metal-
protecting paints).
• Tin
– SnO2 (jewelry abrasive)
 Halides
• SnCl2
– Good reducing agent.
• Quantitative analysis of iron ores.
• SnCl4
– Formed from Sn and Cl2, obtained recovering Sn.
• SnF2
– Anti-cavity additive to toothpaste.
 Oxides
• Lead
– PbO, litharge, yellow (ceramics, cements,
batteries).
– PbO2, red brown (matches, storage batteries).
– Pb3O4, mixed oxide known as red lead, red (metal-
protecting paints).
• Tin
– SnO2 (jewelry abrasive)
 Lead Poisoning

• Extensive use of Pb in plumbing systems, utensils, pottery

glazes and paints, and gasoline additives.
• Pb interferes with heme metabolism.
• Mild poisoning:
– Nervousness and depression.
• Severe poisoning:
– Nerve, brain and kidney damage.
 GROUP IV ELEMENTS

C
Si
Ge
Sn
Pb
• Properties vary through this group.
• Tin and Lead are metallic
– +2 and +4 oxidation states
–  and  forms,  less stable < 13 C, tin pest or tin
disease.
• Germanium is metalloid.
• Silicon, though a semiconductor is mainly
nonmetallic.
• Carbon is a nonmetal.
 CARBON
• 12C isotope (predominantly)
• 13C (smaller amt)

• 14C (radioactive)

– archeological dating
– radioactive tracers
• 1st 4 Ionization Energies (much higher)
 CARBON
• Diamond (extremely unreactive @ rt)
• Graphite (layer structure) reacts more readily
– oxidized to mellitic acid C6(CO2H)6 {hot conc.
HNO3}
– active reducing agent
– reacts readily with many oxides
• liberate the element
• form carbide.
 CARBIDES
3 types which are similar
• Most polar (ionic) {electropositive metals}
• Most covalent (molecular) {electronegative
non – metals}
• Somewhat complex (interstitial) {elements in
the center of the d-block}
 Salt – like carbides
• Be2C and Al4C3 - sometimes called
“methanides”
– yield predominantly CH4 on hydrolysis
• C2 units are well known e.g. acetylides
(ethynides) of alkali metals MI2C2, alkaline
earth metals MIIC2 and the lanthanides LnC2
and Ln2C3 i.e. Ln4(C2)3
• Gp. IB (Cu, Ag, Au) are explosive
• Gp. IIB (Zn, Cd, Hg) are poorly characterized
 Salt – like carbides
• MI2C2 - colourless crystalline compounds
– react violently with water
– oxidized to carbonate on being heated in air
• CaC2 - most important compound
– production of ethyne (chemical industry & oxy -
acetylene welding)
– fixing N2 from air to give calcium cyanamide
{CaCN2}
• widely used as a fertilizer
 Interstitial Carbides
• Lanthanides form
– metal rich carbides M3C {normal carbides (LnC2)}
• Actinides form
– monocarbides MC (several early T. elements)
Which are infusible, extremely hard, refractory
materials that retain many characteristic
properties of metals
 Interstitial Carbides
• C atoms occupy octahedral interstices in a
closed-packed lattice of metal atoms
• Carbides of Cr, Mn, Fe, Co and Ni
– profuse in number
– complicated in structure
– great industrial importance e.g. cementite Fe3C
(important constituent of steel)
– Much more reactive than the interstitial carbides
of the earlier T.S.
 HYDRIDES AND HALIDES
• Catenation - best illustrated in the hydrides (organic
chemistry)
• Replacement of H by F as in CF4
– greatly increases both thermal stability & chemical
inertness
• great strength of the C-F bond
• Thus, fluorocarbons
– resistant to attack by acids, alkalis, o. agents, r. agents and
most chemicals up to 600 oC
– Immiscible with both water & hydrocarbon solvents
– when combined with other groups
• confer water-repellance and stain resistance
– paper, textiles & fabrics
 OXIDES
• Forms 2 extremely stable oxides - CO & CO2
• 3 oxides of considerably lower stability (C3O2,
C5O2 and C12O9)
• number of unstable or poorly characterized
oxides like C2O, C2O3
 OXIDES
• Tricarbon dioxide C3O2
– foul-smelling gas
– from dehydration of malonic acid @ reduced
pressure over P4O10 at 140oC
– polymerizes at rt to a yellow solid
O=C=C=C=O
– readily rehydrates to malonic acid, CH2(CO2H)2
– reacts with NH3&HCl to give amide & acid chloride
CH2(CONH2)2 and CH2(COCl)2
 CYANIDES
• Cyanogen (CN)2
– colourless poisonous gas (like HCN)
– possessing considerable thermal stability (800 oC)
when pure
– presence of trace impurities normally results in
polymerization at 300-500 oC to paracyanogen
with a condensed polycyclic structure
 SILICON

• 28Si (92%) with ~5% 29Si & 4% 30Si

• more volatile than C
– substantially lower energy of vaporization (smaller
Si - Si bond energy)
• Semiconductor
– distinct shiny, blue – grey metallic lustre
 SILICON
• Massive crystalline form
– relatively unreactive except at high t.
– Formation of very thin continuous, protective surface
layer of SiO2 makes rxn with O2, water and steam, less
effective
– Oxidation in air - not measurable below 900 oC
– between 950-1160 oC rate of formation of vitreous
SiO2 rapidly increases
– at 1400 oC, N2 in air gives SiN & Si3N4
– Sulphur vapour reacts at 600 oC
– P vapour reacts at 1000 oC
– unreactive towards aq. Acids
– conc. HNO3 / HF oxidizes & fluorinates the element
 SILICON
• Molten Si (in contrast)
– extremely reactive
• forms alloys or silicides with most metals
• rapidly reducing most metal oxides
– very large heat of formation of SiO2 (900 kJ mol-1)

• Silicon does not form binary compounds with

Ge, Sn, & Pb
• compound with C - SiC
– outstanding academic & practical interest
 SILICON CARBIDE
• Greater thermal stability than any other binary
compound of Si
– decomposition by loss of Si appreciable @ 2700 oC
• resists attack by most aq. acids (HF inclusive but
not H3PO4)
• oxidized in air only above 1000 oC {protective SiO2
layer}
– removed by molten hydroxides or carbonates thereby
accelerating oxidation.
• SiC + 2NaOH + 2O2 = Na2SiO3 + H2O + CO2
 SILICIDES
• All A-subgroup metals except Be
• greatest range Gps IVA – VIII (TMs) &Uranium
• No B-subgroup metals except Cu
• Gps. IA & IIA Silicides generally much more
reactive than those of transition elements
– Hydrogen and/or silanes are typical products
Na2Si + 3H2O  Na2SiO3 + 3H2
Mg2Si + 2H2SO4(aq)  2MgSO4 + SiH4
 SILICIDES
• Formulae cannot be rationalized by
application of simple valence rules
• Bonding varies
– essentially metallic to ionic & covalent
• Observed stoichiometries include
– M6Si, M5Si, M4Si, M15Si4
– M3Si, M5Si, M2Si, M5Si3
– M3Si2, MSi, M2Si3
– MSi2, MSi3, MSi6
 SILICON HYDRIDES (SILANES)
• Silanes, SinH2n+2
– known as unbranched & branched chains (upto n = 8)
– no cyclic compounds or unsaturated analogues of
alkenes and alkynes
– colourless gases or volatile liquids
– extremely reactive
• spontaneously igniting or exploding in air
– Thermal stability decreases with increasing chain
length
• only SiH4 is stable indefinitely at rt.
 SILICON HYDRIDES (SILANES)
• Much more reactive than the corresponding C
compounds
– (a) larger radius of Si which would facilitate
nucleophilic attack
– (b) great polarity of Si-X bonds
– (c) presence of low-lying d – obitals which permit
formation of 1:1 & 1:2 adducts
• thereby lowering the activation energy of the rxn
 SILICON HYDRIDES (SILANES)
• Pure silanes do not react with pure water or
dilute acids in silica vessels
• but even traces of alkali dissolved out of glass
apparatus catalyze the hydrolysis
– which is rapid and complete (SiO2.nH2O + 4H2)
• Solvolysis with MeOH can be controlled
– several products SiH4-n (OMe)n (n=2,3,4)
• Explodes in the presence of Cl2 or Br2
• rxn with Br2 can be moderated at –80o
– good yields of SiH3Br & SiH2Br2
 SILICON HALIDES
• Si & SiC react readily with all halogens
– colourless volatile reactive products SiX4
• Two different tetrahalides heated together
– they equilibrate to form a random distribution of
silicon halides
nSiX4 + (4-n)SiY4 = 4SiXnY4-n
• Higher homologues SinX2n+2
– volatile liquids or solids
• Catenation in Si compounds reaches its
maximum in the halides rather than the hydrides
(contrary to C)
 SILICON HALIDES
• Ascribed to additional back-bonding
– from filled halogen pπ obitals into the Si dπ
orbitals
• synergically compensation for electron loss from Si via
σ bonding to the electronegative halogens
• Fluoropolysilanes
• up to Si16F34
• up to at least Si6Cl14 and Si4Br10 are known
 SILICA
• Chemically resistant to all acids except HF
• Dissolves slowly in hot conc. alkali & more rapidly
in fused MOH or M2CO3
– M2SiO3
• Among halogens, only F2 attacks SiO2 readily
– SiF4 + O2
• Reaction of SiO2 with the oxides of metals &
semimetals
– great interest & importance in glass technology &
ceramics
 SILICATES
• Alkali metal carbonates fused with silica
(~1300o)
– CO2 + complex mixture of alkali silicates
• Basic unit of structure is SiO4 tetrahedron
– Occur singly or by sharing oxygen atoms, in small
groups, in small cyclic groups, in infinite chains or
in infinite sheets
• few simple discrete SiO44- orthosilicate anions
are known e.g. Be2SiO4
 SILICATES
• Simplest condensed silicate anion -
pyrosilicate ion Si2O76- formed by combining
two SiO4 tetrahedra with sharing of O atoms
e.g. Sc2Si2O7
• Cyclic silicates are known Si3O96- and Si6O1812-
e.g. BaTiSi3O9 and Be3Al2 Si6O18
• Infinite chain anions such as (SiO32-)n and
(Si4O116-)n are known.
 GERMANIUM, TIN AND LEAD
• Notable Pair wise similarities in I.Es
– Si & Ge (filling of 3d10 shell)
– Sn & Pb (4f14 shell)
• Ge
– brittle, grey –white lustrous crystals with diamond
structure
– metalloid with similar electrical resistivity to Si at rt
– mp, bp & associated enthalpy changes are also lower
than for Si
• Trend continues for Sn & Pb
– very soft, and low-melting metals
 CHEMICAL REACTIVITY AND TRENDS
• Ge
– more reactive and more electropositive than Si
– dissolves slowly in hot conc. H2SO4 & HNO3
– does not react with water or with dil. acids or alkalis
• unless an oxid. agent like H2O2 or NaOCl is present
– fused alkalis react to yield germanates
– oxidized in air at red heat GeO2
– H2S & S(g) yield GeS2
– Cl2 & Br2 yield GeX4 on moderate heating
– HCl gives both GeCl4 & GeHCl3
– Alkyl halides react with heated Ge (as with Si) to give
organogermanium halides
 CHEMICAL REACTIVITY AND TRENDS
• Sn
– notably more reactive & electropositive than Ge
• though still markedly amphoteric in its aq chemistry
– stable towards both water & air at ordinary temps
– reacts with steam to give SnO2 + H2
– heating in air or O2 gives SnO2
– Dil HCl and H2SO4 show little, if any, rxn
– dil HNO3 produces Sn(NO3)2 & NH4NO3
 CHEMICAL REACTIVITY AND TRENDS
• Sn
– Hot conc HCl yields SnCl2 + H2
– hot conc H2SO4 forms SnSO4 + SO2.
• Occurrence of SnII compounds in these rxns is notable
• By contrast, hot aq alkali yield hydroxostannate (iv)
compounds e.g
Sn + 2KOH + 4H2O K2[Sn(OH)6] + 2H2
• Reacts readily with Cl2 and Br2 in the cold, F2 & I2 on
warming to give SnX4
• reacts vigorously with heated S & Se, to form SnII & SnIV
chalogenides
– depending on the proportions used
• with Te gives SnTe.
 CHEMICAL REACTIVITY AND TRENDS
Finely divided Pb powder is pyrophoric
• reactivity is greatly diminished by formation of
a thin, coherent protective layer of insoluble
prd like oxide, oxocarbonate, sulphate or
chloride
• F2 reacts at rt to give PbF2
• Cl2 gives PbCl2 on heating
• Molten Pb reacts with the chalcogens to give
PbS, PbSe & PbTe
 CHEMICAL REACTIVITY AND TRENDS
• steady trend towards increasing stability of MII
rather than MIV compounds (Ge, Sn, Pb) - “inert
pair effect” {heavier B subgroup metals}
• Notable exception is the organometallic
chemistry of Sn & Pb which is almost entirely
confined to the MIV state
• Catenation is also impt for Ge, Sn, Pb chemistry
thought less so than for C & Si
• Ability of both Sn & Pb to form polyatomic cluster
anions of very low formal oxidation state (e.g
M52-, M94- etc)
– reflects the tendency of heavier B subgroup elements
to form chain, ring or cluster homo-polyatomic ions
 HYDRIDES AND HYDROHALIDES
• Germanes, GenH2n+2
– colorless gases or volatile liquids for n=1-5
– prepn , physical propts and chemical rxns very
similar to those of silanes
– though they are less volatile and noticeably less
reactive
– GeH4 does not ignite in contact with air (cf. SiH4 &
SnH4) & unaffected by aq acid or 30% aq NaOH
– acts as an acid in liq NH3 -> NH4+ + GeH3- ions
– alkali metals in liq NH3 -> MGeH3
 HYDRIDES AND HYDROHALIDES
Germanuim hydrohalides GeHxX4-x (X = Cl, Br, I;
x = 1,2,3)
• colourless, volatile, reactive liquids
– valuable synthetic intermediates (cf SiH3I) e.g.
hydrolysis of GeH3Cl yields O(GeH3)2
SnH4
• decomposes slowly to Sn + H2 at rt
• unattacked by dil aq acids or alkalis but
decomposed by more conc solns
• Potent reducing agent
 HYDRIDES AND HYDROHALIDES
• Sn2H6
– even less stable
• higher homologues not known
• By contrast, organotin halides are more stable
• catenation up to H(SnPh2)6H has been
achieved
PbH4
• least well characterized Gp IVB hydride
• unlikely that it has ever been prepd
 HALIDES
• Ge, Sn & Pb forms two series: MX2 & MX4
• PbX2 more stable than PbX4 whereas reverse is
true for Ge
• steady increase in stability thus:
CX2 << SiX2 < GeX2 < SnX2 < PbX2
• lighter members - colourless, volatile liquids
• GeI4 - orange solid (cf. CX4, SiX4)
• All hydrolyse readily
• GeCl4 - impt intermediate
– organogermanium compounds (LiR or RMgX)
 HALIDES
• SnX2 forms complex series
 presence of non-bonding e-s (5s2) result in
increase in coordination no.
– polymerization to rings or chains
– adduct [SnX2.(NMe3)] (X = Cl, Br, I)
– sometimes double adduct [BF3{SnX2(NMe3)}] (X =
Cl, Br, I) formation
• SnX4
– volatile liquids or solids comprising tetrahedral
molecules except
– SnF4 (unlike CF4, SiF4 & GeF4) is polymeric
• octahedral coordination about Sn
 HALIDES
• PbX2 - much more stable thermally & chemically
than PbX4
• PbF4 - only stable tetrahalide
• PbCl4 - stable below Oo ,but PbCl2 + Cl2 above 50o
• PbBr4 - even less stable
• PbI4 – doubtful
• PbX2 - stable crystalline compounds
– prepd from water soluble PbII salts & halide ions
or HX  ppt insoluble PbX2
 OXIDES
• GeO - reducing agent
– disproportionates rapidly to Ge + GeO2 above 700
o

• Impressive resemblance - oxide chemistry of

GeIV & SiIV
– Ge analogues of all the major types of silicates and
alumino-silicates have been prepd
• SnO oxidized to SnO2 (heated in air to 300o)
• disproportionates {GeO}(heated in absence of oxygen)
• mixed valence oxides e.g. Sn3O4 i.e. SnII2SnIVO4
 OXIDES
• SnO2(cassiterite)
– insoluble in water and dil acids or alkalis
– dissolves readily in fused alkali hydroxides
• “stannates” MI2 Sn(OH)6
• Conversely Hydrous tin (iv)oxide (white ppt)
– readily soluble in both acids and alkalis
• amphoteric nature of SnIV
 OXIDES
• PbO & mixed valence oxide Pb3O4
• PbO2 decomposes when heated

PbO2293oPb12O19351oPb12O17
374oPb3O4605oPbO
• Pb2O3
– obtained by decompn of PbO2 (or PbO) at 580-
620o under O2 pressure of 1.4 kbar.
 Tin and Lead Ores and Uses
• Cassiterite ore, SnO2, reduced with C to Sn.
• Galena, PbS, roasted in air then reduced with C.
• Alloys of Sn
– Solders
– Bronze (90% Cu, 10% Sn
– Pewter (85% Sn, 7% Cu, 6% Bi, 2% Sb)
• Pb
– Pimary use in storage batteries.
– Radiation shields.

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 44 of 47

 Oxides
• Lead
– PbO, litharge, yellow (ceramics, cements,
batteries).
– PbO2, red brown (matches, storage batteries).
– Pb3O4, mixed oxide known as red lead, red (metal-
protecting paints).
• Tin
– SnO2 (jewelry abrasive)

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 45 of 47

 Oxides
• Lead
– PbO, litharge, yellow (ceramics, cements,
batteries).
– PbO2, red brown (matches, storage batteries).
– Pb3O4, mixed oxide known as red lead, red (metal-
protecting paints).
• Tin
– SnO2 (jewelry abrasive)

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 46 of 47

 Halides
• SnCl2
– Good reducing agent.
• Quantitative analysis of iron ores.
• SnCl4
– Formed from Sn and Cl2, obtained recovering Sn.
• SnF2
– Anti-cavity additive to toothpaste.

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 47 of 47

 Lead Poisoning
• Extensive use of Pb in plumbing systems, utensils, pottery
glazes and paints, and gasoline additives.
• Pb interferes with heme metabolism.
• Mild poisoning:
– Nervousness and depression.
• Severe poisoning:
– Nerve, brain and kidney damage.

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 48 of 47