Introduction to transition metal

chemistry and nuclear chemistry

Introduction to transition metal
chemistry
 1st row transition metals
 The elements of the 1st transition series
are those for which the 3d electron shell
contains between one and nine electrons.

 They are often called transition elements

because their position in the table is
between the s and p block element.
• Atoms or ions of these elements have
partially filled d-orbitals.

• These include
Scandium Sc 21 [Ar] 3d14S2

Titanium Ti 22 [Ar] 3d24S2

Vanadium V 23 [Ar] 3d34S2

Chromium Cr 24 [Ar] 3d54S1

Manganese Mn 25 [Ar] 3d54S2

Iron Fe 26 [Ar] 3d64S2

Cobalt Co 27 [Ar] 3d74S2

Nickel Ni 28 [Ar] 3d84S2

Copper Cu 29 [Ar] 3d104S1

• In the atoms of the elements, the 3d
and 4S have similar energy and on
ionization, the neutral atom losses
the 4S electron first since the 3d
orbital are the most stable.
• There is an additional stability conferred
when 3d orbitals are either half filled or
fully filled e.g. the configuration of
chromium and copper have 3d5 4s1
instead of 3d4 4s2 and 3d10 4s1 instead of
3d9 4s2 respectively because of the
additional stability associated with half
filled orbital and fully filled orbital.
• This also explains why Fe2+(3d6) is easily
oxidized to Fe3+(3d5) and why Mn2+(3d5) is
not readily oxidized to Mn3+(3d4).
Properties of transition elements and ions
1). The metals are dense and have high
melting and boiling point due to strong inter
atomic bonding which involves the
participation of both 3d and 4s electrons.
(2). Majority of the transition metal ions are
coloured e.g. Vanadium compounds vary in
colour depending on their oxidation states
V5+(Orange), V4+(blue), V2+(violet)
• V3+[vanadium (III)], Fe2+, Ni2+---------are all
green
• Cr3+,Mn3+-----violet
• Mn3+, Co2+----pink
• Fe3+------Yellow
• Cu2+-----blue
• Their colours are associated with
incompletely filled d-orbitals.
3). The transition elements form complex ions
with polar molecules known as ligands.
• Ligands are negatively charged or contain
donor atoms. For example N, O, S, P which
donate lone pair of electrons. Examples of
ligands are NH3, CN-, Cl- e.t.c.
• [Co(NH3)6]3+---Hexaamine cobalt(III) ion
• [CuCl4]2- --------tetrachloro cuprate(II) ion
When the ligands are easily removed, the
complex is said to be unstable. Stable
complexes have ligands which are difficult
to remove.

(4). They exhibit variable oxidation state

due to successive ionization energies of
transition atoms which increase gradually.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3 4 5 6 7 6 4 4 2 2
3 4 3 6 3 3 2
2 3 2 4 2 2
2 3
2
5). They exhibit catalytic activity in their
compounds which is associated with their
variable oxidation state. Typical catalyst are
vanadium(v) oxide, finely divided
iron(Haber’s process) and Nickel(catalytic
Hydrogenation)
6). The ions exhibit paramagnetism.
Substances may be repelled by a strong
magnetic field(diamagnetism) or
attracted(paramagnetism).
Paramagnetism occurs because the
substance contains unpaired electron while
diamagnetism occurs in substance with
paired electrons.
• Magnetic moment gives information about
the number of unpaired electrons in
transition elements.
• It can be calculated using the formula
• μs = √n(n+2) B.M.
Where n = the number of unpaired electrons
e.g. Sc3+ = d0
n=0
√0(0+2)=0
• Ti3+ d1 n=1
μs = √1(1+2)=√3 =1.73B.M.
Exercise: Cu2+, Ni2+, Co2+, Fe2+, Mn2+.
Metallic character
• In the d-block elements, the penultimate
shell of electrons is expanding.
• They have many physical and chemical
properties in common.
• Thus all the transition elements are metals.
• They are therefore good conductors of
electricity and heat, have a metallic lustre
and are hard, strong and ductile.
Variable Oxidation state
• One of the most striking features of the
transition elements is that the elements
usually exist in several different oxidation
states.
• Furthermore, the oxidation states change
in units of one e.g. Fe3+ and Fe2+, Cu2+ and
Cu+.
• The oxidation states shown by the
transition elements may be related to their
electronic structures.
• Thus Sc could have an oxidation number of
(+II) if both s electrons are used for
bonding and (+III) when two s and one d
electrons are involved.
• Ti has an oxidation state +III when both s
electrons are used for bonding, +III when
two s and one d electrons are used and +IV
when two s and two d electrons are used.

• Similarly, V shows oxidation numbers +II, +III

+IV and +V. In the case of Cr, by using the
single s electron for bonding we get an
oxidation number +I: hence by using varying
oxidation states of +II, +III, +IV, +V, +VI and
+VII.
• Among these first five elements, the
correlation between electronic structure and
minimum and maximum oxidation states in
simple compounds is complete.

• In the highest oxidation states of these first

five elements, all of the s and d electrons are
being used for bonding.
• Once the d5 configuration is exceeded i.e.
in the last five elements, the tendency for
all the d electrons to participate in bonding
decreases. Thus Fe has a maximum
oxidation state of +VI.
Density
• The atomic volumes of the transition
elements are low compared with elements
in the neighbouring group 1 and 2.
• This is because the increased nuclear
charge is poorly screened and so attracts
all the electrons more strongly.
• Melting and Boiling points
The melting and boiling points of the
transition elements are generally very high.
Transition elements typically melt above
1000°C.
Ionization Energies
The ease with which an electron may be
removed from a transition metal atom is
intermediate between those of the s- and p-
blocks.
Colours
The colours of d-block metal compounds are
characteristic feature of species with ground
state electronic configurations other than d0
and d10. for example, [Cr(H2O)6]2+ is sky
blue, [Co(H2O)6]2+ pink, [MnO4]- intense
purple and , [CoCl4]2- dark blue.
• In contrast salt of Sc(III) d0 is colourless.
The fact that many of the observed colours
are of low intensity is consistent with the
colour originating from electronic d-d
transitions.
• Electrons in a partially filled d-orbital can
absorb visible light and move to slightly
higher d-orbital energy levels.
• As a result, many transition metal
compounds have strikingly beautiful
colours (d-d transitions).
• Exceptions are transition metal ions that
have either empty d or a filled d-orbital
e.g. Sc3+ 4s0 3d0; Ti4+ 4s0 3d0.
• These ions are colourless/white and are
diamagnetic.
SIZE OF ATOMS AND IONS
• The covalent radii of the elements decrease
from left to right across a row in the
transition series until near the end when
the size increases slightly.
• On passing from left to right, extra protons
are placed in the nucleus and extra orbital
electrons are added
• The orbital electrons shield the nuclear
charge incompletely (d electrons shield less
efficiently the p-electrons, which in turn
shield less efficiently than s electrons).
• Because of this poor screening by d-
electrons, the nuclear charge attracts all of
the electrons more strongly; hence a
contraction in size occurs.
 Coordination compounds
Examples
[Ni(NH3)6]2+
[Cu(H2O)6]2+
[Cr(acac)3]
[Fe(CN)6]4-
Types: neutral, cationic or anionic.
• Coordination compound is a compound
consisting of a central metal ion or atom
surrounded by and datively bonded to
other ions or molecules called ligands.
These compounds could be neutral,
cationic or anionic.
• NiCl2 dissolves in NH3 to give
NiCl2 + 6NH3[Ni(NH3)6]2++2Cl-
• CuSO4 + 6H2O[Cu(H2O)6]2+ +SO42-
blue
• These ions or molecules or groups bonded
to the central metal are called ligands or
donor molecules since they donate a
pair of electron to form a coordinate bond.

• There are two types of these ligands, the

anionic ligand and neutral ligand. These in
turn, can also be monodentate, bidentate
or polydentate.
• Ligands that contain two or more atoms,
each of which simultaneously form a 2e-
donor bond to the same metal ion are
called bidentate.

• These ligands are also called chelate ligands

since they appear to grasp the cation
between the two or more donor atoms.
ANIONIC LIGANDS
MONODENTATE (UNIDENTATE)
Ligand Donor atom Ligand
symbol name
F- F- fluoro
Cl- Cl- chloro
Br- Br- bromo
I- I- iodo
OH- O hydroxo
Ligand Donor Ligand
symbol atom name
SCN- S thiocyanato
NCS N isocyanato
CH3COO- O Acetato
CN- C Cyano
CO32- C Carbonato
SO42- S Sulphato
Ligand Donor atom Ligand
symbol name
O2- O Oxo
H- H Hydrido
NO2- N Nitro
ONO O Nitrito
NO3- N Nitrate
O2- O Peroxo
BIDENTATE AND POLYDENTATE ANIONIC
LIGANDS
Ligand Symbol Ligand
name

acac acetylacetonate
Carbonate
OX OXALATE
EDTA Ethylenediamine tetraacetate
NEUTRAL LIGANDS
MONODENTATE (UNIDENTATE)
• H2O aquo
• NH3 ammine
• CO carbonyl
• NO Nitrosyl
• RNH2 Amine
• Py- Pyridine
• DMF- Dimethyl formamide
• CH ΞCH – ethyne
• C6H6 – Benzene
• CH2=CH2 – Ethylene
Bidentate/Multidetate Neutral
Ligands

en
ethylenediamine
 Bipy Bipyridine

phen 1,10-Phenanthroline
• Preparation of Coordination compounds
A wide variety of methods are used in
synthesizing coordination compounds and
water is most frequently used as a solvent but
actually plays a part in chemical reaction
leading to complex formation.
• The various techniques employed in the
synthesis include the following
(1). Aqueous substitution reactions
Here a coordinated ligand is substituted with
another ligand and the coordination number
of the metal in the starting material
(reactant) is unchanged in the final product
The most frequently used method of
preparation is the replacement
(Substitution) of H2O molecules by other
ligands in the stepwise fashion which may,
or may not be complete in the presence of
excess ligand.

[Cu(H2O)6]2+ + 4NH3
[Cu(NH3)4(H20)2]2+
+ 4H2O
Cu(II) salts undergo stepwise
replacement and complete substitution
does not occur in aqueous solutions
because of high concentration of water.
For neutral ligands such as organic
molecules, preparation involve the
dissolution of the reactant in alcohol
before mixing.
[Fe(H2O)6]2+ + 3bipy [Fe(bipy)3]2+
+ 6H2O
When the H2O in aquo complexes are
substituted by anions, we can produce neutral
or anionic complexes.
• [Cr(H2O)6]3+ + 3acac- [Cr(acac)3] + 6H2O
• Fe(H2O)6]2+ + 6CN- [Fe(CN)6]4- + 6H2O
• 2). Addition Reaction
• This involves an increase in the coordination
number of the metal and the
transformation of the product may involve a
change in colour.
• [Cu(acac)2] + 2py [Cu(acac)2Py2]
• 2 kinds of valences, a primary valence
and a secondary valence.
• the primary valence -oxidation number-
is satisfied by negative ions.
• secondary valence -the coordination
number
• is satisfied by both negative ions and
neutral molecules
Pt(NH3)6 ]Cl4
[Pt(NH3)4Cl2] Cl2
Old formula Modern formula No o f No of
ions free
C l -
ions
PtCl4.6NH3 [Pt(NH3)6] Cl4 5 4

PtCl4.4NH3 [Pt(NH3)4Cl2] Cl2 3 2

PtCl4.3NH3 [Pt(NH3)3Cl3] Cl 2 1

PtCl42.NH3 [Pt(NH3)2Cl4] 0 0
[Pt(NH3)6 ]Cl4 = [Pt(NH3)6]4+ 4Cl-

[Pt(NH3)4Cl2] Cl2= [Pt(NH3)4Cl2]2+ 2Cl-

[Pt(NH3)3Cl3] Cl = [Pt(NH3)3Cl3]+Cl-

[Pt(NH3)2Cl4] =
 [Pt(NH3)2Cl4]

NH3
Cl Cl

Pt
Cl NH3 Cl
[Pt(NH3)6 ]Cl4 = [Pt(NH3)6]4+ 4Cl-

[Pt(NH3)6]4+=let Pt be equal to X
X+(6x0)= +4
X+0=+4
X=+4
Oxidation number of Pt = 4 in [Pt(NH3)6]4+
[Pt(NH3)4Cl2] Cl2= [Pt(NH3)4Cl2]2+ 2Cl-

[Pt(NH3)4Cl2]2+=
X+(4x0)+(-1x2)=+2
X+0-2=+2
X-2=+2
X=+2+2=+4
Oxidation no of Pt=+4
[Pt(NH3)3Cl3] Cl = [Pt(NH3)3Cl3]+Cl-
[Pt(NH3)3Cl3]+ =
X+(3x0)+(-1x3)=+1
X+0-3=+1
X-3=+1
X=+1+3=+4
Oxidation no of Pt=+4
[Pt(NH3)2Cl4] =

X+(2x0)+(-1x4)=0
X+0-4=0
X-4=0
X=+4
Oxidation no of Pt=+4
• DISCOVERY OF COMPLEXES
• Alfred Werner in a study on Cobalt (III)
and Pt(IV) ammines was able to show
conclusively the structure of coordination
compounds.
• According to Werner, a metal atom
exhibits 2 kinds of valences, a primary
valence and a secondary valence.
• In modern terminology, the primary
valence is what is now called the
oxidation number of the metal and this
is satisfied by negative ions.
• The secondary valence corresponds to
what is now called the coordination
number and is satisfied by both
negative ions and neutral molecules.
• The substance previously represented
by the formula PtCl4.6NH3 is composed
of the ion [PtNH3)6]4+, with six ammonia
molecules directly attached to the
platinum atom.
• The charge of this ion is balanced by
four Cl- ions, giving a neutral compound
with the structural formula
[Pt(NH3)6]Cl4.
• Table below lists a series of platinum (IV)
complexes studied by Werner. It gives
both the old and Werner’s modern
formulas.
• Note that square brackets are used in
modern formulas.
• According to Werner’s theory, these
complexes should dissolve to give
different numbers of ions per formula
unit. For example, [Pt(NH3)4Cl2]Cl2
dissolves to give three ions:
[Pt(NH3)Cl2]2+ and two Cl- ions.
• Werner was able to show that the
electrical conductances of solutions of
these complexes were equal to what
was expected for the number of ions
predicted by his formulas.
• He also demonstrated that the chloride
ions in the platinum complexes were of
two kinds: those that could be
precipitated from solution as AgCl using
silver nitrate and those that could not.
• He explained that the chloride ions
within the platinum complex ion are
securely attached to the metal atom and
that only those outside the complex ion
can be precipitated with silver nitrate.
The number of free Cl ions (those not
attached to platinum) determined this
way agreed exactly with his formulas.
Old formula Modern formula No of No of
ions free
Cl-
ions
PtCl4.6NH3 [Pt(NH3)6] Cl4 5 4

PtCl4.4NH3 [Pt(NH3)4Cl2] Cl2 3 2

PtCl4.3NH3 [Pt(NH3)3Cl3] Cl 2 1

PtCl4.2NH3 [Pt(NH3)2Cl4] 0 0
• Similarly, CoCl3(NH3)6 was also found to
be ionic and it possesses a complex
cation [Co(NH3)6]3+ in which the cobalt
(III) ion is sited at the centre of an
octahedral arrangement of six ammonia
molecules, the three chlorides are
present as free ions.
• Further members of this group of
compounds include CoCl3(NH3)5 and
CoCl3(NH3)4. One or two chloride ions
are directly bonded to the metal ion
(structures 2 and 3); the remaining
chloride ions are non-coordinated.
 3+
NH3
H3N NH3
-
Co 3Cl

H3N NH3 NH3

 2+
NH3
H3N NH3
-
Co 2Cl

H3N Cl NH3
 +
Cl
H3N NH3
-
Co Cl

H3N Cl NH3
In each of [Co(NH3)6]Cl3, [Co(NH3)5Cl]Cl2
and [Co(NH3)4Cl2]Cl, the primary valence
or oxidation state of the cobalt centre is
+3, but the coordination number is six.
Coordination No
The coordination Number is the number
of donor atoms attached to the metal
ion. It is also the number of bonds to the
central metal atom.
• For example, in the complex
[Cu(H2O)4]2+ the copper is surrounded
by the four oxygen atoms that belong
to water molecules, so the
coordination Number of Cu2+ in this
complex is 4.
• Similarly, the coordination Number of
Cr3+ in the [Cr(H2O)6]3+ ion is 6, and the
coordination number of Ag+ in
[Ag(NH3)2]+ is 2.
• Sometimes, the coordination number is
not immediately obvious from the
formula of the complex. For example,
there are many polydentate ligands
which contain more than one donor
atom that can bind simultaneously to a
metal ion.
Often, a metal is able to accommodate
two or more polydentate ligands to give
complexes with formulas such as
[Cr(en)2(H2O)2]3+and [Cr(en)3]3+.

en=
In each of these examples, the
coordination number of the Cr3+ is 6.
In the [Cr(en)3]3+ ion, there are three
ethylenediamine ligands that each supply
two donor atoms, making a total of 6, and
in [Cr(en)2(H2O)2]3+, the two
ethylenediamine ligands supply a total of
4 donor atoms and the water molecules
supply another 2: again the total is six.
FACTORS AFFECTING COORDINATION
NUMBERS
1). Oxidation state of central metal
• The higher the oxidation state, the more
ligands that can be accommodated e.g. M4+
accommodates more ligands than M3+.
• The higher the charge of the metal, the
more deficient in electron, the higher the
tendency to accommodate more ligand.
2). Electronegativity of the ligands
• More electronegative ligand favour higher
coordination number.
3). Size and stearic effect
• The larger the central atom, the more
ligands it can accommodate and the
smaller the ligand size, the more the
ligands around the central atom.
• Large central atom is more common
with transition metals, Lanthanides and
Actinides e.g. Molybdenum, Tungsten
and Rhenium all have coordination
number up to 8 in cyano complexes.
Mo(CN)84-
4). Orbital Energies
• Orbital energies level increases as we
move from hydrogen through helium to
higher element. The more the orbitals
available, the more the chances of
having more coordination number.
5). High metal charge and low ligand charge
favour high coordination number e.g. halides
favour high coordination number than O2- .
• STRUCTURES OF COORDINATION
COMPOUNDS
• In addition to the number of ligands
surrounding a metal, it is important
to know the arrangement of the
ligands i.e. the coordination
geometry.
• There is a definite correspondence
between coordination geometry and
coordination number.
• It is the coordination number that
determines the geometry.
Coordination No 2
• This coordination number is relatively
rare, occurring mainly with the +1
cations of Cu, Ag, Au and with Hg2+.
The coordination geometry is linear.
• Examples include the ions
[H3N-Ag-NH3]+, [NC-Ag-CN]- and
[Cl-Au-Cl]-
• Such complexes are typically unstable
towards the addition of further ligands

• [Cu(CN)2]- + 2CN- [Cu(CN)4]3-

Coordination number 3
The most important geometries for
complexes with coordination number 3
are trigonal planar and trigonal
pyramidal. Examples are the planar HgI3-
and [Cu(CN)3]2- and the pyramidal SnCl3-.
Coordination no 4: Four fold
coordination results in either a square
planar or a tetrahedral structure. Square
planar complexes are formed by Ni(II),
Cu(II) and Pt(II) among others.

Tetrahedral geometry is displayed by

some of the complexes of Zn(II), Cd(II)
and Hg(II).
Coordination No 5: The coordination
number is less common than 4 or 6. The 2
most symmetrical coordination geometries
are the trigonal bipyramid and the square
pyramid.
 Coordination 6: This is the most common
Coordination Number for complex ions.
These complexes are mostly octahedral in
shape and are formed by, among other
elements, Cr(III), Co(III), Pt (IV), and Mo(V)
 Coordination no 7
Arrangement of donor atoms
around the metal center can give
rise to Pentagonal bipyramidal.
The less common arrangements
are monocapped trigonal prismatic
and monocapped octahedral.
High coordination numbers (≥ 7)are
observed most frequently for ions of
the early second and third row d
block metals and for the Lanthanides
and actinides.
Among binary metal halides and
pseudo halides, 7coordinate
structures are exemplified by the
pentagonal bipyramidal ions [V(CN)7]4-
and [NbF7]3-.
 Coordination no 8
Arrangement of donor atoms around
the metal center can give rise to
dodecaheral, square antiprismatic,
and hexagonal bipyramidal.
The less common arrangements are
cube and bicapped trigonal prismatic.
 Square antiprismatic coordination
environments occur in [Zr(acac)4](d0)
and in the in the anions in the salts
Na3[TaF8] (d0) and K2[ReF8](d1)
[Mo(CN)8]3-, [W(CN)8]3-, [Mo(CN)8]4-, or
[W(CN)8]4- possess square antiprismatic or
dodecahedral structures depending on the
cation.
Hexagonal bipyramid is a rare coordination
environment but may be favoured in
complexes containing a hexadentate
macrocyclic ligand.
 Coordination no 9
The coordination geometry is
tricapped trigonal prismatic.
The anions [ReH9]2- and [TcH9]2- (both
d0) provide examples of 9 coordinate
species in which the metal centre is in
a tricapped trigonal prismatic
environment.
A coordination number 9 is most often
associated with yttrium, Lanthanum and
the f-block elements. The tricapped
trigonal prism is the only regular
arrangement of donor atoms yet observed,
e.g. in [Sc(H2O)9]3+, [Y(H2O)9]3+ and
[La(H2O)9]3+,
Structure of Common Coordination
Complexes
Coordination no Shape Examples
2 [Ag(NH3)2]+
[Cu(CN)2)-
Linear
Coordination no Shape Examples
4 [Cd(CN)4]2-
[FeCl4]-
[Ni(CO)4]

[MnO4]-
[Zn(NH3)4)2+

Tetrahedral
Coordination no Shape Examples
4 [Ni(CN)4]2-

[Pt(NH3)4]2+
[Cu(NH3)4)2+
[Au(NH3)4]3+

Square Planar
Coordination no Shape Examples
6 [Co(NH3)6]3+,
[PtCl6]2-
[CoF6]3-,
[MoF6)-

Octahedral
The phenomenon of Radioactivity
The term radioactivity was proposed by
Marie Curie to describe the emission of
ionizing radiation by some of the heavier
elements.
• All substances are made of atoms. They
have electrons (e) around the outside
and a nucleus in the middle.
• The nucleus consists of protons (P) and
neutron (n), and is extremely small.
• A force called the binding force holds
both the protons and neutrons together
in the nucleus. If this binding force
holding protons and neutrons together is
strong, the atom is said to be stable.
• The stability of this nucleus depends on
its proton/neutron ratio.
• If this ratio is high, the nuclei are said to
be unstable and will decay into a more
stable one. This radioactivity decay is
completely spontaneous.
• When an unstable nucleus decays, there
are three ways that it can do so. It may
give out
• An alpha particle 
• A beta particle 
• A gamma ray 
• Many radioactive substances emit 
particles and -particles as well as -
rays. A pure  source cannot be found,
anything that gives off  rays will also
give off  and/or .
• -Particles
• Alpha particles are made of 2protons
and 2neutrons. This means that they
have charge of +2 and a mass of 4.
• Alpha particles are relatively slow and
heavy.
• They have a low penetrating power.
• They can be stopped by a thin sheet of
paper.
• Because they have a large charge, alpha
particles ionize other atoms strongly. 
particles are ejected at extremely high
velocities from the nuclei of heavier
unstable elements.
238 U234 Th
92 90 + 42He + 
• As a result of this emission, of an -
particle, the atomic number of the
nucleus decreases by 2 and the mass
number by 4.
-Particles
• Beta particles have a charge of minus 1
• They are fast moving electrons.
• -particles are ejected from the
unstable nuclei of atoms at velocities
approaching that of light.
234 Th234 Pa
90 91 + 0-1e + 
• The loss of a -particle does not affect
the mass number of the nucleus but
increases its atomic number by 1.
• Beta particles have a medium power of
penetration and they are stopped by a
thin sheet of aluminum or plastics such
as Perspex.
• Beta particles ionize atoms that they
pass, but not as strongly as Alpha
particles do.
-rays
• Gamma rays are waves, and not
particles.
• This means that they have no mass and
no charge.
• It is emitted by nuclei with excess
energy and generally accompanied by
 or -particles.
238 U234 Th
92 90 + 42He + 
• Gamma rays have a high penetrating
power and it takes a thick sheet of metal
such as lead, or concrete to reduce
them significantly.
Write nuclear equations to represent
a). α particle emission by 22286Rn
b). Radioactive decay of bismuth-215 to
polonium
Solution
We can identify two of the species
involved in this process simply from the
information given.
We can deduce the remaining species by
using the basic principles of expression.
Note that as long as a name or chemical
symbol is given such as Rn, the atomic
number of the element follows directly.
222 Rn ? + 4 He
86 2
222 Rn 218 Po + 4 He
86 84 2

b). Bismuth has the atomic number 83, and

polonium 84. The type of emission that leads
to an increase of one unit in atomic number is
β-.
215 Bi 215 Po + 0 e
83 84 -1
Naturally occurring Radioactive Isotopes
209 Bi is the nuclide of highest atomic and
83
mass number that is stable. All known
nuclides beyond it in atomic and mass
numbers are radioactive. Naturally
occurring 23892U is radioactive and
disintegrates by loss of α particles.
238 U234 Th + 4 He + 
92 90 2
• 234 Th
90is also radioactive; it decay is by β-
emission.
234 Th234 Pa + 0 e + 
90 91 -1

• 234 Pa also decays by β-

91 emission.
234 Pa234 U + 0 e + 
91 92 -1
The radioactive decay of U-238 to thorium
results in a loss of an -particle and the
emission of -radiation which can
represent a 1st step in one particular
sequence of radioactive decay
238 U234 Th + 4 He + 
92 90 2
• 238 U
92spontaneously decays in a series
of steps until the stable element 206Pb is
formed.
• The heavy radioactive elements may be
grouped into four decay series, the
common radioactive elements thorium,
uranium and actinium occur naturally
and belong to three different series
named after them.
• They are the parent members of their
respective series and have the longest
half life periods. They decay by a series
of , and  emissions and produce
radioactive elements which are
successively more sable until finally a
stable isotope is reached.
• All the three series terminate with lead
(20682Pb, 20782Pb and 20882Pb). Following
the discovery of the artificial post-
uranium elements, the neptunium series
has been added, which ends with
bismuth, 20993Bi.
• Thorium (4n) series
• Neptunium (4n+1) series
• Uranium (4n+2) series
• Actinium (4n+3) series
• The number in bracket indicate that the
parent and all the members of a
particular series have mass number
exactly divisible by four, or divisible by
four with a remainder of one, two or
three.
Each time an -particle is emitted, the
mass no decreases by 4 and the atomic
number decreases by 2 and each time a -
particle is emitted, the mass number
remains the same but the atomic number
increases by 1.
238 U α 234 Th β 234 234 U
92 90 91Pa β 92 α

230 Th α 226 Ra α 222 Rn α 218 Po α

90 88 86 84

214 Pb β 214 Bi β 214 210 Pb

82 83 84Po α 82 β

210 Bi β 21084Po α 20682Pb

83
The sequence of radioactive decay stable
isotope from to 23892U to 20682Pb
Radioactive decay of tritium
3 H 3 He + 0 e + 
1 2 -1
Tritium decays by -emission to form a
stable isotope of helium.
Half Life
The half life is the amount of time it takes
for half of the atoms in a sample to decay.

The half life for a given isotope is always

the same; it does not depend on how
many atoms.
• The half life is the time taken for the
number of radioactive nuclei to be
reduced to half.

• The rate of radioactive decay varies

greatly from one radioisotope to
another.
• For a single radioactive decay process,
the number of nuclei which disintegrate
in a short time period depends only on
the relative number of radioactive
atoms present.
• Thus the size of the sample does not
affect the time taken to undergo
radioactive decay.

• The half life is the same no matter what

the size of the sample, the temperature
or any other external condition.
• t½ = 0.693/k.
Radioactive decay is a typical exponential
decay. The amount of radioactive
substance left during decay can be
related to its initial amounts by the
following equation.
• N=Noe-kt Where N is the amount left
• No is the initial amount
• k is a constant
• t is the time taken for the decay.
• The decay rate, or activity of a
radioactive substance are
characterized by constant quantities.
• Half life – symbol t½ - i.e. time for half
of a substance to decay.
• Decay constant – symbol λ
• Mean life time – symbol - the average
lifetime of any given particle.
Example: A radioactive element has an
initial count rate of 1400 counts per second
measured by a proportional counter and
this falls to 1800 counts per minutes in
5hours.
(i). Calculate the half life of the radioactive
element.
(II). If the initial number of atoms in
another sample of this element is 4.5x1019,
how many atoms has decayed in 28 hours.
• Initial count rate, No=1400cps
• New count rate after 15 hours,
Nt=1800cpm=30cps
• t= 15hours= 15x60x60s= 54,000s
Using equation
In Nt = -λ t
No
λ = -1 x InNt
t No
λ = -1 x In30
54000 1400
λ =7.12x10-5s-1
t1/2=0.693
λ
=0.693 =
7.12x10-5s-1
t1/2= 9.73 x103s-1
In Nt = -λ t
No
Nt = e-λ t
No
Nt=Noe-λ t
λ=7.12x10-5 s-1
t=28 hours=28x60x60=100800 s
Nt= 4.5x1019 e[-7.12x10-5 x100800]
=4.5x1019 x7.65x10-4=3.44x1016atoms
• Amount that have decayed is
= Initial amount of atoms-number remaining
undecayed
= No-Nt=4.5x1019 - 3.44x1016atoms
= 4.496x1019atoms
2). An old human skull was unearthed in an
archaeological excavation at Ogbomoso and its
14 C/12 C ratio was only 0.326 of that in the
6 6
atmosphere today. How old is the skull, if the
half life of 146C is 5,700yrs.
Solution
Nt ratio is 146C/126C = 0.326
No
t1/2=0.693
k
t1/2=0.693
k
k = 0.693 = 0.693
t1/2 5,700yrs
k = 1.22x10-4 yr-1
Using equation
In Nt = -k t
No
t = In Nt ÷ -k
No
= -1 x In 0.326
1.22x10-4 yr-1
= 9.19x103 years
1).A stick from an ancient tomb was found
to have a 146C content that gave 10.7
d/min/g. A living plant gives 15.3 d/min/g
and t1/2 for 146C is 5770 years. How old is
the stick.
2). Complete the following nuclear equations.
• i). 23090Th 22688Ra + ?
• ii). 24194Pu24195Am + ?
• iii). 22286Rn21884Po + ?
• iv). 21583Bi21584Po + ?
• v). 23892U 23490Th + ?
• vi). 21483Bi  21484Po + ?
A radioactive nuclide that has an atomic
number of 88 and a mass (nucleon)
number of 226 is used in radiation
therapy. Write its nuclide symbol in the
form of AZX. Write two other ways to
represent this nuclide.
226 Ra 226Ra radium -226
88
A radioactive nuclide with the symbol
40 K is used for geologic dating. What is
19
the atomic number and mass(nucleon)
number? Write two other ways to
represent this nuclide.
Atomic number =19
mass (nucleon) number= 40
40K potassium-40
Uses of radioactive decay
• Nuclear power plant
• Age dating
• Radioactive tracers
• Cancer treatment
• Sterilizing
• Smoke detectors
• Genetic studies
1). Radioactive decay has been put to use
in the technique of radioisotopic labelling,
used to track the passage of a chemical
substance through a complex system
(such as a living organism)
Radioactive isotopes such as iodine-131 and
phosphorus -32 can be used as tracers for the
detection of the metabolic path of an element
in an organism. Thus, the metabolism of that
organism could be studied.
In medical diagnosis and treatment,
iodine 131 (a , and  emitter) with a half
life of 8 days is a useful tool for diagnosing
thyroid disease. In agriculture, phosphate
labelled with radioactive P-32 can easily
traced by Gerger-Muller tube.
2). The phenomenon of radioactive decay
allows the evaluation of the age of very
ancient objects into precision (bone,
pottery, cave painting) or date major
events in the earth’s history (volcanic
eruptions, climate change).
3). Another application of radioactivity as
in the production electricity in nuclear
power plants.
4). Radiotherapy
Radiation changes the matter that
absorbs It, modifying its physical and
chemical properties. Radiation destroys
certain cancerous cells. This fact is used
in radiotherapy, a technique that allows
many cancers to be cured.
It is also used in the food industry to
destroy bacteria, thus improving the
preservation of certain foods.
The process is called ionization. It does
not make the foods radioactive but
renders them more wholesome and
increases their shelf life.