Introduction

An element: is the simplest form of a substance. Generally, it cannot be simplified or broken

down further into smaller particles.
An atom: is the smallest unit into which matter can be divided without the release of
electrically charged particles. -The smallest building unit of matter-

▪ What is difference between monatomic and diatomic molecular elements?

Monatomic elements exist in nature as stable single atoms, whereas diatomic molecules
exist in nature as a molecule of two atoms (H2 - N2 - F2 - O2, - I2 - Cl2 - Br2).
▪ What is difference between molecules and compounds?
A molecule is a group of two or more similar atoms held together by chemical bonds,
whereas a compound is a substance which is formed by two or more different types of
elements. - All molecules are not compounds-

Periodic Table of Chemical Elements

 Dmitri Mendeleev and Lothar Meyer were the two chemists that came up with the
periodic law.
 Chemical elements are organized in rows (called periods) and columns (called groups or
families) according to increasing atomic number.
 The atomic number is the Basis for the Periodic Law.
 The atomic number: is the number of protons in the nucleus of an atom which is always
equal to the number of electrons in the neutral atom (e- loss or gain form ions).
The number of protons is distinct for each element
 Elements with the most similar properties were placed in the same group.
 Short form periodic table
A table where elements are arranged in 7 rows with increasing atomic numbers from left
to right and there are 18 vertical columns known as groups.
 Long form Periodic Table
Each period correlates to the building up of electronic shell; the first two groups (1-2) (s-
block) and the last 6 groups (13-18) (p-block) make up the main-group elements and the
groups (3-12) in between the s and p blocks are called the transition metals. Group 18
elements are called noble gases, and group 17 are called halogens. The f-block elements,
called inner transition metals, which are at the bottom of the periodic table (periods 8 and
9); the 15 elements after barium are called lanthanides and the 14 elements after radium
are called actinides.
 Scientists use the periodic table to quickly refer to information about an element, like
atomic mass and chemical symbol.

 The periodic table’s arrangement also allows scientists to discern trends in element
properties, including electronegativity, ionization energy, and atomic radius.

 An atom is made up of three subatomic particles: protons, neutrons, and electrons.

› If you change the number of protons, you completely change the element.
› If you change the number of electrons, you create ions. A loss of electrons is going to
lead to an anion. A gain of electrons is going to lead to a cation.
› If you change the number of neutrons (change atomic mass), you create isotopes.
› Isotopes: are variants of chemical elements that possess the same number of protons
and electrons, but a different number of neutrons.
 Electron Configurations
▪ The electron configuration of an element describes how electrons are distributed in its
atomic orbitals.
▪ The electron configuration of an atom is written with the help of subshell labels.
▪ The electron configuration is used to determine valence level/electrons.
▪ By knowing the valence level we determine the main energy level and the number of
electrons in it and based on them we can know the group/place in periodic table.

Filling of Atomic Orbitals:

Aufbau Principle
› This principle is named after the German word ‘Aufbeen’ which means
‘Build up’.
› The Aufbau principle dictates that electrons will occupy the orbitals
having lower energies before occupying higher energy orbitals.
› According to this principle, electrons are filled in the following order:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p

› the s, p, d, and f subshells can accommodate a maximum of 2, 6, 10, and 14 electrons,

respectively.
The electron configuration of phosphorus atom:

- Valence level: [ 3S, 3P] Row No. 3

- No. of e- in valence level = 5 Column No. 5

Hund’s Rule
› This rule describes the order in which electrons are filled in all the orbitals belonging to a
subshell.
› It states that every orbital in a given subshell is singly occupied by electrons before a
second electron is filled in an orbital.
› Atoms with half-filled or completely-filled orbitals are comparably more stable.
› In order to maximize the total spin, the electrons in the orbitals that only contain one
electron all have the same spin (or the same values of the spin quantum number).

 Electron spins in two directions; Spin up and Spin down

 Pauli Exclusion Principle
› This principle states that a maximum of two electrons, each having opposite spins, can
fit in an orbital.
› No two electrons in the same atom have the same values for all four quantum numbers.
› Therefore, if the principal, azimuthal, and magnetic numbers are the same for two
electrons, they must have opposite spins.

▪ What are Quantum Numbers?

The set of numbers used to describe the position and energy of the electron in an atom.
 The four quantum numbers: principal (n), azimuthal (l), magnetic (m) and spin (s).
 Introduction to the d-Block Elements
Transition element: is defined as the one which has incompletely filled d orbitals in its ground
state or in any one of its oxidation states.
 d- block elements are named (transition elements) as the d–block elements occupy
the middle of the periodic table and their properties are transitional between s– and p–
block elements.
▪ Transition metals are found in nature
› Rocks and minerals contain transition metals
› The color of many gemstones is due to the presence of transition metal ions:
- Rubies are red due to Cr
- Sapphires are blue due to presence of Fe and Ti
› Many biomolecules contain transition metals that are involved in the functions of
these biomolecules:
- Vitamin B12 contains Co
- Hemoglobin, myoglobin, and cytochrome C contain Fe
▪ Transition metals and their compounds have many useful applications:
› Fe is used to make steel and stainless steel
› Ti is used to make lightweight alloys
› Transition metal compounds are used as pigments:
TiO2 = white
PbCrO4 = yellow
Fe4[Fe(CN)6]3 (Prussian blue)= blue
› Transition metal compounds are used in many industrial applications.
The d-block elements: elements present in the middle of the periodic table from Group 3 to 12.
 They are the four rows of elements in the periods 4th (3d series), 5th (4d series),
6th (5d series) and 7th (6d series).
 The name d- blocks because the last electron enters into the d-orbital.
 d- block elements are named as transition elements as they occupy the middle of the
periodic table and their properties are transitional between s– and p– block elements.
• The d-block elements include:
First transition series or 3d series (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn)
Second transition series or 4d series (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd)
Third transition series or 5d series (La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg)
  Most have partially occupied d subshells in common oxidation states.

Electronic Configuration of D Block Elements

• The general electronic configuration of d block elements is [ Noble gas] (n-1)d1-10 nS1-2
• The general outer electronic configuration of d- block elements is (n-1)d1–10 nS1–2

• The electronic configuration for period 4, transition elements is (Ar) 4s 1-2 3d 1-10
• The electronic configuration for period 5, transition elements is (Kr) 5s 1-2 4d 1-10
• The electronic configuration for period 6, transition elements is (Xe) 6s 1-2 5d 1-10

▪ Zinc, cadmium and mercury of group 12 are not regarded as transition metals as
transition metals are defined as the elements having incompletely filled d orbitals in ground
state or any common oxidation state. Since Zn, Cd and Hg have completely filled d orbital in
ground state and common oxidation states; they are not regarded as transition elements.

▪ We can say that Sc (Z = 21) is a transition element but Zn (Z = 30) is not as

On the basis of incompletely filled 3d orbitals in case of scandium atom in its ground state
(3d1), it is regarded as a transition element. On the other hand, zinc atom has completely
filled d orbitals (3d10) in its ground state as well as in its oxidized state, hence it is not
regarded as a transition element.
▪ In first transition series [Sc (21) to Zn (30)]:
Chromium has a 4s1 3d5 electron configuration rather than a 4s2 3d4 electron
configuration, while copper has a 4s1 3d10 electron configuration rather than a 4s2 3d9.

 The stability of half-full orbitals relative to partially filled orbitals explains these
oddities in the first transition series.

▪ In second transition series [Y (39) to Cd (48)]:

In the second series, from niobium, s-orbital has mostly only one electron as s and d-
orbital have the almost same energy, because of which electrons prefer to occupy the d-
orbital.

 The stability of half-full orbitals relative to partly filled orbitals explains these
oddities in the second transition series.

▪ In third transition series [La (57) to Hg (80)]:

In 5d series, all elements except Pt and Au have filled s-shell.
Third series transition metals have more paired s configuration even at the expense of
half-filled orbitals (Tungsten- 6s25d4) because the high shielding of d orbitals by the ‘f’
electrons (lanthanide contraction) increases the energy gap between the s and 5d orbitals
such that pairing energy is less than the excitation thus excitation of the electron does not
take place in tungsten, in spite of the stability possible because of half-filled orbitals.

Gold Au 79 [Xe] 4f14 5d10 6s1

 The stability of half-full orbitals relative to partly filled orbitals explains these
oddities in the third transition series.
› Characteristic properties exhibited by d-block elements due to their partly filled
d orbitals:
1. Display of a variety of oxidation states,
2. formation of colored ions and
3. entering into complex formation with a variety of ligands.
 General Properties of the d-Block Elements and Their Trends
1. Atomic radii of elements of all three-transition series:
Atomic radius: is the total distance from the nucleus of an
atom to the outermost orbital of its electron.

Atomic radii of elements of all three-transition series:

• Decreases rapidly, from column 3 to 6
• Remains steady, from column 7 to 10 and
• Starts increasing from column 11 to 12.

• The larger decrease in atomic radii, in column 3 to 6

elements is due to the increase in effective nuclear charge but poor shielding because of
the smaller number of d-electrons.

• In elements of column 7 to 10 increasing effective nuclear charge is balanced by the

repulsion between the shared d electrons so that radii remain the same.

• In the case of 11 and 12 columns elements, the d orbital is full with ten electrons and
shield the electrons present in the higher s-orbital. So, groups 11 and 12 elements like Cu
and Zn have bigger sizes than their earlier elements.
• Size does not appear to increase significantly between fifth and sixth period elements.
 This phenomenon is associated with the intervention of the 4f orbitals which must be
filled before the 5d series of elements begin. The filling of 4f before 5d orbital results
in a regular decrease in atomic radii called lanthanide contraction.
  The electrons in 4f orbitals are not very good at screening valence electrons from the
nucleus. Thus, the strength of attraction of valence electrons to the nucleus is greater
than expected in the sixth period.

2. Melting point of elements of all three-transition series:

• The transition metals (with the exception of Zn, Cd and Hg)
are very hard and have low volatility.
 Their melting and boiling points are high.
 These elements have moderate to high melting points and
moderately high densities.
• Electrical and thermal conductivities of these elements are
very high.
 Copper is second only to silver in electrical conductivity.
• Fig. 8.1 depicts the melting points of transition metals belonging to 3d, 4d and 5d
series.
 The melting points of the transition metals in a series rise to a maximum at the
middle of the series (i.e., Cr or Mo or W - element with d5 configuration) and fall
regularly as the atomic number increases.
 The high melting points of these metals are attributed to the involvement of greater
number of electrons from (n-1)d in addition to the ns electrons in the interatomic
metallic bonding.
o Metallic bonding is a type of chemical bonding that arises from the
electrostatic attractive force between conduction electrons (in the form of
an electron cloud of delocalized electrons) and positively charged metal
ions.
• When we move from left to right in the periodic table in a transition series, the
number of unpaired electrons increases up to configuration d5.
 Therefore, the strength of metallic bonds in d-block increases, along with the
melting point.
• By taking the first transition series into account, we can conclude that the melting
point increases from Sc to Cr. Then, Mn shows a low melting point, which breaks the
series of events. This is because the metallic bond is weak in comparison to the bond
of other d-block elements as the 3d electrons do not participate in metallic bonding.
  As we proceed further, the melting points decrease due to the decrease in the
number of unpaired electrons.

 Zn, Cd, and, Hg are soft and have low melting point it is due to the absence of
unpaired electrons in Zn, Cd, and, Hg, thus the formation of the strong metallic
bond is not possible.
• The slight increase in the melting point of Fe as Fe+3 (unpaired electrons) is one of the
strongest known elements.

• In the fourth-period d-block, only scandium is active enough to displace H2 from

H2O.

3. Ionization Energy of D Block Elements:

Ionization energy: is the amount of energy required to remove the lowest
bonded electron from an atom in gases state. (+ve charge).

Electron affinity: is the amount of energy liberated when an electron is added to a

neutral atom to form a negatively charged ion.

• Ionization Energy of the d block elements is larger than

s-block and smaller than the p-block elements, between
which, they are placed.

• In the first series, the ionization energy of d block

elements increases with the increase in atomic number
up to Fe.
- Chromium (Cr) and copper (Cu) have notably larger ionization energy than
their neighbors due to the extra stability associated with the half-filled and
fully-filled set of d-orbitals.
- In Co and Ni, IE decrease as the increasing sharing of d-electrons compensate
for the atomic number increase.

 In the second series, elements from Niobium show a gradual increase in IE with
increasing atomic number as they have single electrons in the s-orbital
- Palladium (Pd) shows the maximum IE as it has a completed d-shell and no
electron in the s-shell.
In the third series: ionization energy of 5d elements is much larger than 4d and 3d
because of lanthanide contraction (the attraction of electrons by the nuclear charge
is much higher).
- Elements from Hafnium to rhenium have the same IE (due to sharing only the
s-electrons) and after IE increases with the number of shared d-electrons such
that Iridium and Gold have the maximum IE.
→ In the periodic table, Atomic radii decrease from left to right across a row and increase from
top to bottom down a column.
 Because of these two trends, the largest atoms are found in the lower left corner of the
periodic table, and the smallest are found in the upper right corner.

› Atomic radius decreases from left to right within a period. This is caused by
the increase in the number of protons and electrons across a period. One proton has a
greater effect than one electron; thus, electrons are pulled towards the nucleus,
resulting in a smaller radius.
› Atomic radius increases from top to bottom within a group. This is caused by electron
shielding.

→ Trends in atomic size decrease from left to right across a row and increase from top to
bottom down a column.
 It results from differences in the effective nuclear charges experienced by electrons in
the outermost orbitals of the elements.
 For all elements except H, the effective nuclear charge is always less than the actual
nuclear charge because of shielding effects.
 The greater the effective nuclear charge, the more strongly the outermost electrons
are attracted to the nucleus and the smaller the atomic radius (smaller size).

→ Trends in Ionization energy increases from left to right across a row and decrease from top
to bottom down a column.

› The ionization energy of the elements within a period generally increases from left to
right due to valence shell stability.
› The ionization energy of the elements within a group generally decreases from top to
bottom due to electron shielding.
› The noble gases possess very high ionization energies because of their full valence
shells as indicated in the graph. Note that helium has the highest ionization energy of
all the elements.
 In general, ionization energy increases as effective nuclear charge (Zeff) increases –
Exceptions occur due to the stability of specific electron configurations.
 This is because the atomic radius generally decreases moving across a period, so
there is a greater effective attraction between the negatively charged electrons and
positively-charged nucleus.
  The noble gas has a filled valence shell, so it resists electron removal.

→ Trends in Electron affinity increases from left to right across a row and decrease from top
to bottom down a column.
› Electron affinity increases from left to right within a period due to the decrease in
atomic radius.
› Electron affinity decreases from top to bottom within a group due the increase in
atomic radius.
 As elements trend to the right, the added electrons sit closer to their nuclei. These
electrons exhibit a stronger attraction to the nuclei as a result of this proximity,
explaining the exothermic nature of their electron affinities.
 As we travel down a group, elements contain electrons further from their nuclei, and
these electrons are bound less tightly thus do not release as much energy upon joining
an atom compared to their tightly bound counterparts.

→ Trends in Metallic character decreases from left to right across a row and increase from top
to bottom down a column.
› Metallic characteristics decrease from left to right across a period due to the decrease
in radius (caused by Zeff, as stated above) of the atom that allows the outer electrons
to ionize more readily.
› Metallic characteristics increase down a group. Electron shielding causes the atomic
radius to increase thus the outer electrons ionizes more readily than electrons in
smaller atoms.

› Metallic character relates to the ability to lose electrons, and nonmetallic character
relates to the ability to gain electrons.
›
→ Trends in oxidation state of transition metals increases with increase in atomic number and
reaches a maximum in the middle and then decreases.
→ Trend in melting points of transition metals in a series rise to a maximum at the middle of
the series (i.e., Cr or Mo or W - element with d 5 configuration) and fall regularly as the
atomic number increases.
▪ Explain the trend in atomic size of 3d series of transition elements with reason.
With increase in atomic number in 3d series - atomic size decreases (Sc to Cr) , then remain
almost constant (Cr to Cu) and increase slightly at the end (Cu to Zn). Reason:
In the beginning of the series the screening (or shielding effect) effect of a d electron is not
that effective, hence the net electrostatic attraction between the nuclear charge and the
outermost electron increases, hence atomic size radius decreases.
In the middle of the series, increase in nuclear charge and increase in screening effect
balance each other. So atomic radii become almost constant.
Increase in atomic radii towards the end is due to the electro – electron repulsions cause the
expansion of electron cloud.

 The apparent anomaly properties at the end of the period resulted from the d
orbital being full with ten electrons and shielding the electrons present in the higher s-
orbital (bigger sizes than their earlier elements).
 Characteristic properties
A) Color:
The complexes of the d-block metal ions are usually colored, except, very often, those of d0
and d10 metal ions.
The colors are due to:
a) Electronic transitions of d-electrons within the d sub-shell.
- These are known as d→d transitions.
- d0 and d10 metal ions do not show these transitions.
 The energy required for d-d electron excitation is available in the visible range.
 Transition metal ions have the tendency to absorb certain radiations from the visible
region and exhibit the complementary colour.
 An unpaired electron(s) is required for the occurrence of d-d transition.
 The transition metal ions which have completely filled d-orbitals are colorless as the
excitation of electron or electrons is not possible within d-orbitals.
 The transition metal ions which have completely empty d-orbitals are also colorless.

 The reason behind this is the crystal field splitting of d-orbitals of the central metal
atom.
- The electrons present in the ground state absorb light in visible range and jump
into a higher energy level and the complementary colors appear.

b) Electronic transitions from the metal ion to the ligand (M→L transitions) or
ligand to the metal ion (L→M transitions), which are known as charge-transfer
transitions, and these can occur for d0 to d10 metal ions.

c) The ligands themselves may be colored, and this color may contribute to the color of
the complex.
d) Crystal defect: defect in the regular spacing of atoms within a solid that absorbs
visible light of a particular colour leads to a characteristic colour in the solid.
B) Paramagnetism:
When there are unpaired electrons in the d sub-shell, these will lead to paramagnetism.
 Paramagnetic property is only shown when the element contains one or more unpaired
electrons in any orbital.
 Transition metals and their compounds shows paramagnetic behavior as the
transition metal ions are generally containing one or more unpaired electrons in
them and hence their compounds are generally paramagnetic.
 The unpaired electrons in (n-1) d orbitals are responsible for the magnetic properties.
 The paramagnetic character of the transition metals increases on moving from left to
right as the number of unpaired electrons increases from one to five.
 The middle elements are found to possess the maximum paramagnetic property.
 The magnetic properties decrease with the decrease in the number of unpaired
electrons.
 To calculate the value of the magnetic moment ϻ = √𝑛(𝑛 + 2) B.M
Calculate magnetic moment of Fe(aq)2+ion(Z=26).

The total number of unpaired electrons, n = 4

Magnetic moment is given by μ=n(n+2)B.M. = √4(4 + 2)𝐵. 𝑀.= √24B.M. = 4.9B.M.

 The value of ϻ is slightly higher than the number of unpaired electrons.

 The metal of the 1st row transition series that has highest value for magnetic moment
is Chromium (Cr) followed by Manganese (Mn).
 The metal of the 1st row transition series that has zero spin only magnetic moment in
its +2 oxidation state is Zinc (Zn).

› Calculate the ‘spin only’ magnetic moment of M2+ (aq) ion (Z = 27).
Solution
Electronic configuration of M atom with Z=27 is [Ar]3d74s2
∴Electronic configuration of M2+ will be [Ar]3d7 , i.e.,
Thus, it has three unpaired electrons.
∴Spin only magnetic moment (μ) = √𝑛(𝑛 + 2) 𝐵. 𝑀. = √3(3 + 2) 𝐵. 𝑀. = √15𝐵. 𝑀.
=3.87B.M.
 › Why is Sc3+ (or Zn2+) diamagnetic?
Sc3+(Z=21) 3d0 no unpaired electron, n=0, μ=0.
(or Zn2+(Z=30) 3d10 no unpaired electron, n=0, μ=0)

- In [Cr(H2O)6]3+ the three d electrons (it is d3) are unpaired. Thus, like the O2
molecule which is paramagnetic, Cr(III) is paramagnetic.
- A d10 metal ion (e.g. Zn(II)) has a filled d sub-shell, and a d0 metal ion (e.g. Ti(IV))
has no d-electrons, so neither of these can be paramagnetic.

C) Variable oxidation states

Most d-block metal ions display variable oxidation states it is due to the fact that (n-1)d
electrons may get involved along with ns electrons in bonding.
- For example, Mn displays oxidation states from:
Mn(-III) (in [Mn(CO)(NO)3]) through Mn(0) (in [Mn2(CO)10]) to Mn(VII) (in [MnO4]-).

 Transition metals and their many compounds act as good catalysts due to
1. Their variable oxidation states.
2. The partially filled (n-1) d orbital
3. Provide a suitable surface for the reaction to take place.

 The lowest oxidation state corresponds to the number of ns orbital electrons thus all
the first-row transition metals except Sc form stable compounds that contain the 2+
ion, and, due to the small difference between the second and third ionization energies
for these elements, all except Zn also form stable compounds that contain the 3+ ion.
 The +2 oxidation state, which commonly occurs for nearly all the transition metals is
due to the loss of their outer 4s electrons.
 Scandium (Sc) does not exhibit variable oxidation states as it has an electronic
configuration [Ar]4s23d1 and it tends to stabilize (empty d-orbital) and thus exhibits a
+3 stable oxidation state by losing the two 4s electrons and the 3d electron.

 The metal of the 1st row transition series that exhibit maximum number of oxidation
states is Manganese (Mn).
 The metal of the 3d series of transition metals which exhibit +1 oxidation state most
frequently is copper (Cu).
 The highest oxidation state shown by 3d series transition metals is +7 by Mn.
  The metal of the 3d series of transition metals that do not show variable oxidation
states is Scandium (Sc).
 Transition metals exhibit variable oxidation states in its compounds due to the
availability of both ns and (n – 1)d electrons for bond formation.
 The metal of the 3d series of transition metals that can’t have 1+ or 3+ oxidation state
is Zinc (Zn) (d fully occupied).
 The metal of the 3d series of transition metals that can’t have 2+ oxidation states is
Scandium (Sc).
 The metal of the 3d series of transition metals that have only 3+ oxidation state is
Scandium (Sc).
 Fe+3 is more stable than Fe+2, the reason is that:
According to electron configuration Fe3+ has half-filled configuration (stable) [Ar]3d5
whereas Fe2+ has Ar]3d6 configuration (less stable).
 Mn2+ is more stable than Mn3+, the reason that:
According to electron configuration Mn2+ has half-filled configuration (stable) [Ar]3d5
whereas Mn3+ has Ar]3d4 configuration (less stable).


Fourth-period d-block elements form ionic bonds with somewhat less ionic character
than do the metals of the s-block.
 Lower oxidation states (+2, +3) usually correspond to ionic character.
  For Co through Zn, relative energies of the 4s and 3d subshells are such that few (or no)
3d electrons are lost in forming ions.
 For Zn, the 4s–3d energy difference is so large that only 4s electrons are lost.

D) Complex-formation:
Transition metals form a large number of complex compounds due to
1. Their Small size
2. High charge density of the ions of transition metals (variable oxidation states).
3. Presence of vacant d orbitals of suitable for bond formation.

The d-block metal ions form a wide variety of complexes, of generally high stability,
with ligands such as EDTA or F-, Cl-, and OH-, or ethylene diamine (en), as well as
many others, much as was the case for the main group metal cations.
Many of the d-block metal ions are powerful Lewis acids, as can be seen by comparison
with some main group element cations:
 Bonding in Transition metal Complex (Coordination)

Central atom/ ion

Ligand: is an ion or molecule (functional group) that binds to a central metal atom to form a
coordination complex.
Coordination number: the number of ligand donor atoms (lone pairs) to which the metal
(central atom/ion) is directly bonded.
Example:
In the complex ions [PtCl6]2-, [Ni(NH3)4]2+and, [Cr(NH3)4]3+ the coordination
number of Pt, Ni and, Cr are 6, 4 and 4 respectively.
Coordination number Shape Bond angle Hybridization
2 Linear 180° sp
3 Triangle planar 120° sp2
4 Square planar 90° dsp2
4 Tetrahedral 109.5° sp3
5 Triangle bipyramidal 120° - 90° dsp3
5 Square pyramidal 90° sp3d
6 Hexagonal 60° d2sp3 or sp3d2
6 Prism 60° d2sp3 or sp3d2
6 Octahedral 90° d2sp3 or sp3d2
 Octahedral shape is more stable than Hexagonal and prism shapes due to the higher
bond angles (Higher BA Lower strain).
 Coordination number 7,8,10,12 is rare.
 Most common coordination numbers are 4 and 6.

Different Hybridization Geometrics

Linear Triangle planar
 Square planar Tetrahedral

Triangle bipyramidal Square pyramidal

Hexagonal Prism Octahedral

Coordination sphere: the central atom/ion and the ligands attached to it are enclosed in
square bracket.
Coordination polyhedron: the spatial arrangement of the ligand atoms which are directly
attached to the central atom/ion (octahedral, square planar and
tetrahedral).
Oxidation number of central atom: the charge left on the central atom when all ligands are
removed along with the electron pairs that are shared
with it.

Oxidation number of central atom calculation

[Cr(NH3)4]3+
Ox. St. of NH3 = 0
X + 0 = 3+ X is the Ox. St. of Cr
X = 3+

K4[Fe(CN)6]0
Ox. St. of CN = -1
Ox. St. of K = 1
(1× 4) + X +(-1 × 6) = 0 X is the Ox. St. of Fe
4+X–6=0
X = 6 – 4 = 2+

Inner hybridization: the central metal atom uses inner shell d orbitals for the hybridization
of atomic orbitals.
 the d orbitals involved in the hybridization are in a lower
energy level than s and p orbitals.

Outer hybridization: the central metal atom uses outer shell d orbitals for the hybridization
of atomic orbitals.
 the d orbitals involved in the hybridization are in the same
energy level as the s and p orbitals.
▪ Only certain elements possess the remarkable property of forming coordination compounds
as it requires small size, high charge density of the ions (variable oxidation states) and
presence of vacant d orbitals of suitable for bond formation.

There are four theories to explain the nature of bonding in coordination compounds:
1. Valence Bond Theory (VBT)
2. Crystal Field Theory (CFT)
3. Ligand Field Theory (LFT)
4. Molecular Orbital Theory (MOT)

Valence Bond Theory (VBT)

According to this theory, the metal ion under the influence of ligands can use its n-1d, ns, np
or ns, np, nd orbitals for hybridization to yield a set of equivalent orbitals of definite
geometry as octahedral, tetrahedral, square planar and so on.

Coordination number Hybridization Distribution of hybrid

orbitals in space
2 sp Linear
3 sp2 Triangle planar
4 dsp2 Square planar
4 sp3 Tetrahedral
5 dsp3 Triangle bipyramidal
5 sp3d Square pyramidal
6 d2sp3 or sp3d2 Hexagonal
6 d2sp3 or sp3d2 Prism
6 d2sp3 or sp3d2 Octahedral

It is usually possible to predict the geometry of a complex from the knowledge of its
magnetic behavior on the basis of the valence bond theory.
Paramagnetic: atoms with unpaired electrons
Diamagnetic: atoms don’t have unpaired electrons.
In the diamagnetic octahedral complex, [Co(NH3)6]3+, cobalt ions is in 3+ oxidation state and
has the electronic configuration 3d6. In the presence of NH3 a strong ligand, the 3d
electrons pair up leaving two d-orbitals empty. Hence, the hybridization is d2sp3 forming an
inner orbital octahedral complex (low spin - spin paired).
The hybridization scheme is as shown in diagram:

 Co3+ion has 4 unpaired electrons in 3d-subshell and NH3

is a strong ligand. Therefore, electrons get paired up

In the formation of this complex, since the inner d orbital (3d) is used in hybridization, the
complex [Co(NH3)6]3+ is called an inner orbital, low spin or spin paired complex.

The paramagnetic octahedral complex {CoF6]3- uses outer orbital (4d) in hybridization
(sp3d2) as F is a weak ligand (no e pair up). It is call outer orbital or high spin or spin free
complex.
The hybridization scheme is as shown in diagram:

 Co3+ion has 4 unpaired electrons in 3d-subshell and F

is a weak ligand. Therefore, NO electrons get paired up

Magnetic properties of coordination compounds:

The magnetic moment of coordination compounds can be measured by the magnetic
susceptibility experiments.
› For metal ions with up to three electrons in the d orbitals, like Ti3+ (d1), V3+ (d2),
Cr3+ (d3+) two vacant d orbitals are available for octahedral hybridization with 4s
and 4p orbitals.
 › When more than 3d electrons are present, the required pair of 3d orbitals for
octahedral hybridization is not directly available (as a consequence of Hund’s
rule). Thus, for d4 (Cr2+, Mn3+), d5 (Mn2+, Fe3+), d6 (Fe2+, Co3+) cases a vacant pair
of d orbitals results only by pairing of 3d electrons which leaves two, one and zero
unpaired electrons, respectively.

The value of magnetic moment based on only rotation on axis can be determined by the
formula BM, where n is number of unpaired electrons.

The spin only magnetic moment of [MnBr4]2– is 5.9 BM. Predict the geometry of the
complex ion:
Since the coordination number of Mn2+ ion in the complex ion is 4, it will be either
tetrahedral (sp3 hybridization) or square planar (dsp2 hybridization), but the fact that
the magnetic moment of the complex ion is 5.9 BM (5 unpaired elections), it should
be tetrahedral in shape rather than square planar because of the presence of five
unpaired electrons in the d orbitals and Br is a weak ligand (No electron pairing).

Predict the geometry of the complex ion [Mn(CN)6]4–

 CN is a strong ligand. Therefore, electrons get paired up

› [Mn(CN)4]4–: inner hybridization (d2sp3)

Low paramagnetic
Low spin complex
Geometry: Octahedral
Predict the geometry of the complex ion [MnCl4]2–
› [MnCl4]2–: Outer hybridization (sp3)
High paramagnetic
High spin complex
Geometry: Tetrahedral
 Crystal Field Theory (CFT)
CFT is an electrostatic model which considers the metal-ligand bond to be ionic arising
purely from electrostatic interactions between the metal ion and the ligand.
Ligands are treated as point charges in case of anions or dipoles in case of neutral
molecules as H2O and NH3.

The 5d orbitals are degenerate. This degeneracy may be symmetrical or asymmetrical

depends upon the nature of the crystal field.
Crystal field theory (CFT) describes the breaking of orbital degeneracy in transition metal
complexes due to the presence of ligands.

Crystal field for octahedral complexes:

In an octahedral coordination entity with six ligands surrounding the metal atom/ions,
there will be repulsion between the electrons in metal d orbital and the electrons of the
ligands.

Thus, the dx2-y2 and dz2 orbitals which point towards the axes will experience more
repulsion and will be raised in energy, and the dxy, dyz and dxz orbitals which are
directed between the axes will be lowered in energy relative to the average energy in the
spherical crystal field.

Thus, the degeneracy of the d orbitals has been removed due to ligand electron-metal
electron repulsions in the octahedral complex to yield three orbitals of lower energy (t2g)
set and two orbitals of higher energy (eg) set.

Crystal field splitting is the splitting of the degenerate levels due to the presence of
ligands in a definite geometry.
The energy separation is donated by ∆o (the subscript o is for octahedral). Thus, the
energy of the two eg orbitals will increase by (3/5)∆o and that of the three t2g will
decrease by (2/5)∆o.
› The crystal field splitting ∆o depends on:
The field produced by the ligand and charge on the metal ion.

Ligand ∆o
Weak small
Strong big
Ligands can be arranged in a spectrochemical series in the order of increasing field strength
as given below:

Crystal Field Splitting Energy, Δo

For configurations d1 – d3 and d8 – d10 there is only one ground state configuration.
For configurations d4 – d7 there are two possible filling schemes depending on the
magnitudes of P and Δo.

A high spin configuration minimizes pairing by spreading the electrons across both the t2g
and eg levels.
A low spin configuration minimizes occupying the higher energy eg level by pairing
electrons in the t2g level.
 Low field strength (Δo < P) results in a high-spin state.
High field strength (Δo > P) results in a low-spin state.

Occupancy of electrons in t2g and eg orbitals results in an overall crystal field stabilization
energy (CFSE), defined for octahedral complexes as
CFSE = (-0.4nt2g + 0.6neg) ∆o + pP
where nt2g = number of electrons in t2g orbitals
neg= number of electrons in eg orbitals
p = total number of electron pairs
P = mean pairing energy
Crystal field for tetrahedral complexes:
In tetrahedral coordination, the d orbital splitting is inverted and is smaller as compared
to the octahedral field splitting.
only high spin configurations are observed.
(i) Δt is much smaller than Δo.
(ii) it can be shown that Δt = (4/9)Δo.
(iii) Δt << P in ordinary complexes, so high spin is favored.

The crystal field stabilization energy for tetrahedral complexes is calculated from the
following equation:
CFSE(Td ) = (–0.6neg + 0.4nt2g )∆t + pP
Crystal field for Square Planner

The strong octahedral field repel the single electron in dx2-y2 orbital make it larger energy
than dz2 and the difference in energy between these orbitals become larger than the energy
needed to pair the electrons so a more stable arrangement arises when both the eg electrons
pair up and occupy the lower eg orbital as

Thus, the four ligands bonding to the metal in a square planner geometry with dsp2
hybridization even with week ligands like water or halides.

The ∆o is larger than paring the metal is more charged or week ligands.
 So Pt(II) and Au(III) are square planner all times.
 Naming of Coordination Compounds
Types of Coordination Complexes:
Cationic complexes: In this co-ordination sphere is a cation.
Example: [Co(NH3)6]3+
Anionic complexes: In this co-ordination sphere is Anion.
Example: [Fe(CH)6]
Neutral Complexes: In this co-ordination sphere is neither cation or anion.
Example: [Ni(CO)4]
Types of Ligands:
Based on the nature of the bond between the ligand and the central atom, ligands are
classified as follows:
Anionic ligands: CN–, Br–, Cl–
Cationic ligands: NO+
Neutral ligands: CO, H2O, NH3, NH2CH2CH2NH2

› The ligands are always written before the central metal ion in the naming of
complex coordination complexes.
Ligand
The neutral ligands’ names (unmodified) in
coordination compounds:
NH3 (ammine),
H2O (aqua or aquo),
CO (carbonyl),
Neutral NO (nitrosyl),
NH2CH2CH2NH2 (ethylenediamine),
C5H5N (pyrimidine)
CH3NH2 (methylamine)
O2 (dioxygen)
N2 (dinitrogen)

Cationic ligand names are the same as the names of

Cationic their neutral compounds. e.g.,
(N2H5+) → Hydrazinium
(NO+) → Nitrosonium
(NO2+) → Nitronium
(C6H5N+H3) → Anilinium
 Anions which end in "-ide" are replaced with an
Anionic ending "-o" e.g.,
Chloride (Cl-) → Chloro
Fluoride (F-) → Fluoro
Bromide (Br-) → Bromo
Iodide (I-) → Iodo
Oxide (O ) → Oxo
2-

Peroxide (O22-) → Peroxo

Superoxide (O2-) → Superoxo
Cyanide (CN-) → Cyano
Isocyanide (NC-) → Isocyano
Hydroxide (OH-) → Hydroxo

Anions ending with "-ite" and "-ate" are replaced

with endings "-ito" and "-ato" respectively e.g.,
Nitrite (NO2-) → Nitrito,
Nitrate (NO3-) → Nitrato,
Sulfate (SO42-) → Sulfato
Thiosulfate (S2O32-) → Thiosulfato
Thiocyanate (SCN-) → Thiocyanato
Acetate (CH3COO-) → Acetato
Carbonate (CO32-) → Carbonato
Oxalate (C2O42-) → Oxalato

› The number of ligands is denoted by a prefix – mono, di, tri, tetra, penta, hexa.
› Metal Oxidation state is denoted by a Roman numeral.
› Ligands are named first in alphabetical order followed by the name of the metal
center and metal oxidation state.
› When there are many ligands present in the coordination compound, the anionic
ligand is written first followed by neutral then cationic.
› After the ligands are named, the name of the central metal atom is written. If the
complex has an anionic charge associated with it; the suffix ‘-ate’ is applied.
 There are exceptions shown in the table below
› If the coordination compound is accompanied by a counter ion, the cationic entity
must be written before the anionic entity.
Formula:
1. is written with metal first, followed by the ligand
symbols in alphabetical order.
2. Cations come first, followed by anion

Name the following complexes

[Cr(H2O)2Br2(NH3)2]1+ Dibromodiamminediaquachromium (III) ion
[Co(CN)6]3- Hexacyanocobaltate (III) ion
K4[Fe(CN)4Br2] Dibromotetracyanoferrate (II)
[Fe(NH3)4Br2]Cl Dibromotetraammineiron(III) chloride
[Cr(NH3)3 (H2O)3]Cl3 Triamminetriaquachromium(III)chloride
[Ag(NH3)2][Ag(CN)2] Diamminesilver(I) dicyanoargentate(I)
[Cr(NH3)5SO4]Cl Pentamminesulfatochromium(III)chloride
[Co(NH3)6][Cr(CN)6] Hexaamminecobalt(III) hexacyanochromate(III)
[Cr(NH3)6][Co(CN)6] Hexaamminechromium(III) hexacyanocobaltate(III)
[Pt(NH3)2Cl(NO2)] Diamminechloronitrito-N-platinum(II)
K3[Cr(C2O4)3] Potassium trioxalatochromate(III)
[CoCl2(en)2]Cl Dichlorobis(ethane-1,2-diamine)cobalt(III) chloride
[Co(NH3)5(CO3)]Cl Pentaamminecarbonatocobalt(III) chloride
Hg[Co(SCN)4] Mercury (I) tetrathiocyanatocobaltate(III)

Write the formulas for the following coordination compounds

Tetra ammine aqua chloro cobalt (III) chloride [Co(NH3)4 (H2O)Cl]Cl2
Potassium tetra hydroxo zincate (II) K2[Zn(OH)4]
Potassium trioxalatoaluminate(III) K3[Al(C2O4)3]
Dichloro bis/di(ethane-1,2-diamine) cobalt(III) [CoCl2(en)2]+
Tetracarbonyl nickel(0) [Ni(CO)4]
Dichloro bis/di(ethane-1,2-diamine) cobalt(III) [CoCl2(en)2]+
▪ The bonds in coordination compounds have directional properties as the atoms bonded
prefer specific orientations in space relative to one another (CFS).

▪ Coordination compounds have characteristic magnetic and optical properties; both the color
and the magnetic properties of a complex can be attributed to the crystal field splitting.

▪ Draw the energy level diagrams of the following ions Ru3+ (d5) in week and strong
octahedral ligand field?
▪ Predict if the result complex is a strong/week paramagnetic or diamagnetic in previous
question and mention the Approximate values of Bohar Magneton/metal ion.

In case of strong ligand, the result complex is low spin, octahedral inner complex - weak
paramagnetic - M= 1.7BM.
In case of weak ligand, the result complex is high spin, octahedral outer complex - strong
paramagnetic - M= 5.9BM.

▪ Draw the energy level diagrams of Ni(II) (d8) in tetrahedral and square planner ligand
field?
▪ Explain on the basis of valence bond theory that [Ni(CN)4]2– ion with square planar
structure is diamagnetic and the [NiCl4]2– ion with tetrahedral geometry is
paramagnetic.
▪ [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral.
Why?
Though both [NiCl4]2− and [Ni(CO)4] are tetrahedral, their magnetic characters are different.
This is due to a difference in the nature of ligands.
Cl− is a weak field ligand and it does not cause the pairing of unpaired 3d electrons. Hence,
[NiCl4]2− is paramagnetic.

In [Ni(CO)4], Ni is in the zero oxidation state i.e., it has a configuration of 3d 8 4s2.

But CO is a strong field ligand. Therefore, it causes the pairing of unpaired 3d electrons.
Also, it causes the 4s electrons to shift to the 3d orbital, thereby giving rise to sp3
hybridization. Since no unpaired electrons are present in this case, [Ni(CO)4] is diamagnetic.
 Scandium group

General properties
› They are hard metals with low aqueous solubility
 (Not used individually but in the form of alloys).
› Low availability to the biosphere.
› No group 3 element has any documented biological role in living organisms.
› The radioactivity of the actinides generally makes them highly toxic to living cells,
causing radiation poisoning.
› Scandium has no biological role, but it is found in living organisms, it concentrates in
the liver, some its compounds are possibly carcinogenic.
› The elements always exist in the oxidation state (+III), and occur as M3+ ions with a
d0 configuration so their compounds are colorless and diamagnetic.
 › The covalent and ionic radii, melting point, and density of the elements increase
regularly on descending the group as in the s block.
› The later groups of transition elements are affected by the lanthanide contraction due
to the 14f -block elements which occur after lanthanum.
› The importance of d-block elements lies in their ability to make alloys with the rest of
the elements and thus create new properties.

› Lanthanum (La) and Actinium (Ac) are placed in the d-Block as

1. According to electronic configuration (La), [Xe]5d1 6s2, and (Ac), [Rn]6d1 7s2,
they do have one electron in a d-orbital and no electrons in f-orbitals outside
their inert gas core, [Xe] and [Rn] respectively.
2. The arrangement of La and Ac below yttrium (Y) in group 3 (IIIB), gives
similar periodic trends in several physical properties (atomic radii, sum of the
first two ionization potentials, and melting point) when comparing the first
three periods of the d-block (6).

Occurrence, Separation and Extraction

› The four elements are sometimes grouped with the fourteen lanthanons and called
collectively the rare earths.
› Yttrium (Y) is the most abundant on Earth when compared to the rest of the group
elements.
› It is difficult to separate compounds of Y and La from those of the lanthanide
elements and it is also difficult to extract the metals from their compounds because
their melting points are high, they react with water, and their oxides are very stable so
that a thermite reaction cannot be used.

› The metals are obtained by reduction of the chlorides or fluorides with calcium at
1000 oC

Chemical Properties
› Gp. 3 metals are quite reactive, and reactivity increases with increased size.
› They burn in oxygen giving oxides M2O3 , and tarnish in air.
› Y forms a protective oxide coating in air, which makes it unreactive.
› They react slowly with cold water, and more rapidly on heating, liberating hydrogen
and forming basic oxides and hydroxides.

› Sc(OH)3 is well established, and is amphoteric like Al(OH)3 while Y(OH)3 and
La(OH)3 are basic.
› Scandium is amphoteric (can react with both acids and bases)., it dissolves in NaOH.

› Y(OH)3 and La(OH)3 react with carbon dioxide (acid).

› Because the oxides (and hydroxides) are either amphoteric or weak bases, their salts
can be decomposed to oxides by heating, in a similar way to Group II elements, but
rather more easily.

› The metals react with the halogens forming trihalides MX3.

 The fluorides are insoluble, and the others are very soluble like CaCl2.
 The anhydrous chlorides can be made from the oxides.

› ScCl3 differs from AlCl3 in:

ScCl3 is monomeric whilst (AlCl3)2 is dimeric and ScCl3 shows no Friedel Crafts
catalytic properties.

› If the chlorides are prepared in solution, they crystallize as hydrated salts.

These hydrates halides decompose on heating, Sc giving the oxide rather than the
anhydrous halide and the others giving oxyhalides.
 › The elements all react with hydrogen on heating to 300 oC, forming compounds of
formula MH3.

› The hydrides react with water, liberating hydrogen, and are salt-like (ionic) hydrides
containing the H- hydride ion.

› Scandium forms carbide ScC2 when the oxide is heated with carbon. The carbide
reacts with water liberating acetylene.

Complex Formation
› The metal ions in this group do not have a strong tendency to form complexes,
because of their fairly large size.
› Scandium is the smallest ion and forms complexes more readily than the other
elements and its complexes are octahedral in shape.

› The complexes of the large metals often have a coordination number greater than six,
for example a coordination number of eight in [La(acetylacetone)3(H2O)2], and a
coordination number of ten in [La.EDTA(H2O)4 ].3H2O.

Common Uses
› Scandium (Sc):
Aluminum-scandium alloys for aerospace industry components
It also used for sports equipment such as bicycle frames, fishing rods, golf iron
shafts and baseball bats.
Scandium iodide is used in mercury vapor lamps, which are used to replicate
sunlight in studios for the film and television industry.
 Titanium group

General properties
Oxidation States
› The most common and most stable oxidation state for all the elements is (+IV).
 The two s and two d electrons are shared with other atoms to form covalent
molecules, which are tetrahedral.
› The (+IV) state is oxidizing while the (+III), (+II), and (+II) states are reducing.
› The oxides MO2 are regarded as ionic, but they are insoluble, and M4+ ions do not
exist in solution.
› In the oxidation state (+IV):
The elements have a d0 configuration, and are consequently diamagnetic, and
typically white or colorless.

› In the oxidation state (+III):

The oxidation state (+III) is reducing, and Ti3+ ions are more strongly reducing
than Sn2+.
 They (M3+) are reasonably stable, and exist as solids and in solution.
Since the M3+ ions have a d1 configuration they have one unpaired electron and are
colored and paramagnetic and the magnetic moments of their compounds are close
to the spin only value of 1.73 BM.
With only one d electron, there is only one possible d-d electronic transition, hence
there is only one band in the visible spectrum, and nearly all the compounds are
purple colored.
Ti(III) is much more basic than Ti(IV), and the addition of alkali to Ti3+ solutions
precipitates Ti2O3 .(H2O)n , which is purple in color and insoluble in excess alkali.

› In The oxidation state (+II):

The (+II) state is very unstable and so strongly reducing that it reduces water,
hence the few compounds known exist only in the solid state.

› The lower oxidation states tend to disproportionate into a higher oxidation state and
a lower state.

Size
› The covalent and ionic radii increase normally from Ti to Zr, but the expected
increase in size from Zr to Hf is almost exactly cancelled by the decrease in size
which occurs because of the filling of the 4f level (lanthanide contraction).
 Since the size of Zr and Hf are almost identical and they have a similar
electronic structure, their chemical properties, too, are almost identical.

Reactivity and Passive Behavior

› The metals are unreactive or passive at low temperatures because of the formation of a
thin impermeable oxide film.
› At room temperature they are unaffected by either acids or alkali.
 However, titanium dissolves slowly in hot concentrated HCI giving Ti3+ ions
and in HNO3 giving TiO2.(H2O)n.

Zirconium dissolves in hot concentrated H2SO4 and aqua regia.

The best solvent for all the metals is HF, because of the tendency to form hexafluoro
complexes.
Ti + 6HF → H2[TiF6] + 2H2

› In contrast the metals are very reactive at temperatures over 600 oC.
 They form oxides MO2, halides MX4, interstitial nitrides MN and
interstitial carbides MC by direct combination.
› The hydrides are stable in air, and are unaffected by water-in marked contrast with
the behavior of the ionic hydrides of the scandium group and s block elements.

› Oxides, oxyions and peroxides

The elements of this group all form very stable ionic dioxides MO2, which are
insoluble in water, nonvolatile, and rendered refractory by strong ignition.

› The halides MX4 can be made from the halogens and metal (at high temp.).
TiCl4 is the best known, and it is made commercially by heating TiO2 with carbon
and chlorine.
TiO2(s) + C(s) + 2Cl2(g) → TiCl4(g) + CO2(g)

The other titanium halides can be prepared from TiCl4 by reaction with the appropriate
hydrogen halide.
TiCl4 + 4HBr → TiBr4 + 4HCl

 TiCl4 is a colorless, diamagnetic, covalent fuming liquid.

 ZrCl4 is a white solid.
 In the gaseous state, all the halides are tetrahedral, but in the solid zigzag
chains of MX6 octahedral exist.
 The tetrahalides act as acceptors to a wide variety of donors, forming a large
number of octahedral complexes.
 The fluorides are more stable than the others.

The halides are all hydrolyzed vigorously by water, and fume in moist air.
  With excess water, hydrolysis is complete for TiCl4, but with ZrCl4 hydrolysis
is incomplete and the oxychloride is stable.
› The halides TiX3 are readily formed by reducing TiX4 compounds.

Occurrence, Extraction, and uses

› Titanium is the ninth most abundant element in the earth's crust, and the main ores
are rutile (one of the three forms of TiO2) and ilmenite FeTiO3.
› Zirconium is relatively abundant and is found as zircon ZrSiO4 and baddeleyite ZrO2
› Hafnium is very similar to zirconium because of the lanthanide contraction, and it
occurs in zirconium ores.
› Titanium has been called the wonder metal because of its unique and useful
properties: It is very hard, high melting,
a good conductor of heat and electricity, and
has better corrosion resistance than stainless steel but is much lighter.

› Ti extraction methods: Kroll process.

I.C.I process.
Van Arkel method.
Electrolysis in an inert atmosphere.

› Common uses:
Titanium metal is used as an alloying agent with metals including aluminum, iron,
molybdenum and manganese.
Alloys of titanium are mainly used in aerospace, aircraft and engines where strong,
lightweight, temperature-resistant materials are needed.
As a result of its resistance to seawater, titanium is used for hulls of ships, propeller
shafts and other structures exposed to the sea.
Titanium is also used in joint replacement implants, such as the ball-and-socket hip
joint.
About 95% of titanium production is in the forum of titanium dioxide (titania).
 This intensely white pigment, with a high refractive index and strong UV light
absorption, is used in white paint, food coloring, toothpaste, plastics and
sunscreen.
Titanium is used in several everyday products such as drill bits, bicycles, golf clubs,
watches and laptop computers.
 Vanadium group
(Group 5 elements)

General properties
Oxidation States
› The maximum oxidation state for this group is (+V).
› Zinc and acid reduces V5+ to V2+ , Nb5+ to Nb3+ and does not reduce Ta5+ .
 This illustrates the increasing stability of the (+V) state, and the usual trend is
that on descending a group the lower oxidation states become less stable and the
higher states more stable.

Size
› The atoms are smaller than those of the titanium group, and because of the lanthanide
contraction, the covalent and ionic radii of Nb and Ta are almost identical.
 Consequently, these two elements have very similar properties, occur together,
and are very difficult to separate.
› V is similar to Ti in that:
It is hard, high melting, extremely corrosion-resistant, and
at room temperature, it is not affected by air, water, alkalis,
or non-oxidizing acids other than HF.
It dissolves in hot concentrated H2SO4, HNO3 and aqua regia.

› Nb and Ta are also very unreactive and resistant to acids except HF, but dissolve in
fused (extreme temp.) alkali.
› At high temperatures the element reacts with many nonmetals.
› The basic properties of the oxides M2O5 increase down the group.
V2O5 is amphoteric but mainly acidic; Nb2O5 and Ta2O5 are more acidic.

Color
› Color in transition metal compounds very commonly arises from:
d-d electronic transitions, but it can also arise from
Defects in the solid state and
Less commonly from charge transfer spectra.
› The (+V) state has a d0 configuration so d-d spectra are impossible. Nevertheless some
(+V) compounds are colored V2O5 because of defects and NbCl5 , NbBr5 and NbI5
because of charge transfer.

Compounds with Nitrogen, Carbon and Halides

› At high temperatures the metals form:
Nitrides MN and two series of carbides MC and MC2
› MC is interstitial, refractory and very hard and the MC2 are ionic and react with water,
liberating acetylene.
› On heating, Nb and Ta react with all the halogens giving penta-halides MX5 , but with
V the oxidation state formed depends on the particular halogen: VF5 , VCl4 , VBr3 VI3 .
› All the halides are volatile, covalent and hydrolyzed by water.

Abundance, Extraction
› V, Nb and Ta have odd atomic numbers and are relatively rare elements.
› They are difficult to extract because of their high melting points and reactivity at high
temperatures.
› Normally an iron/vanadium alloy called ferrovanadium is prepared by a thermite
reaction, and this can then be incorporated into steel alloys.
› Pure vanadium can be obtained by:
- Reducing VCl3 with Na or H,
- VCl4 with Mg (Kroll process) or
by the Van Arkel method (pyrolysis of iodide).
› All three metals can be obtained by electrolysis of molten Fluoro complexes such as
K2[NbF7].

Uses
› Vanadium is an important catalyst in oxidation reactions such as:
Naphthalene → Phthalic acid, and Toluene → Benzaldehyde
› V2O5 is an important catalyst in the manufacture of SO3 by the contact process.
› Nb is used in chromium-nickel stainless steel.
because it is unreactive, and is not rejected by the human body.

› Ta is used for making metal plates, screws and wire for repairing badly fractured bones
because it is unreactive, and is not rejected by the human body.
 Chromium group
(Group 6 elements)

General properties
Oxidation States
› From the electronic structures, Cr and Mo might be expected to from (+I) to (+VI), while
W from (+II) to (+VI).
› For Cr the (+II), (+III) and (+VI) states are well known:
Cr(+II) is reducing and ionic,
Cr(+III) is the most stable and important and
Cr(+VI) is strongly oxidizing.
› Cr(+V) is rare and unstable and occurs only as CrF5, and the peroxide [Cr(O-O)4]3- .
› The most important stated for Mo and W are (+V) and (+VI).
› The zero oxidation state arises in metal carbonyls such as Cr(CO)6, Mo(CO)6 and
W(CO)6 , where the σ bonding electrons are donated by the CO group, and dπ -pπ back
bonding occurs from the filled metal orbitals.
 These carbonyl compounds may be sublimed under reduced pressure, and are
soluble in organic solvents.
› Cr3+ is very stable in acidic solution, it is easily oxidized to Cr+6 in alkaline solution.
› Cr+6 compounds are very strong oxidizing agents and include chromates and dichromats
› The metals are hard and have very high m.p. and low volatility.
› W is the element with the next highest m.p. to C.
› Cr is unreactive at low temperatures because it is protected by a surface coating of
oxide, thus, resembling the behavior of Ti and V.
› Cr dissolve in HCI and H2SO4 , but not in HNO3 or aqua regia, which passivate the
metal.
› Mo and W are relatively inert, and only slightly attacked by aqueous acids and alkalis.
› Mo reacts initially with HNO3 but then becomes passive.

Size
› The atoms are smaller than those of the vanadium group, and because of the lanthanide
contraction, the covalent and ionic radii of Mo and W are almost identical.
 Consequently, these two elements have very similar properties, occur together,
and are very difficult to separate.

Compounds with Nitrogen, Carbon and Halides

› The metals don’t react with oxygen at normal temperatures but on strong heating:
Cr forms Cr2O3, whilst Mo and W form MO3.
 (+VI) Most stable state

› On heating Cr with the halogens, halides CrX3 are formed.

 (+III) most stable state

› Mo and W form MCl6 on heating with chlorine and MF6 is formed at room temperature.

Extraction
› Chromium occurs as the ore chromite FeCr2O4
› Chromium is used in many ferrous alloys, including stainless steel, and for these
purposes, ferrochromium an alloy containing Fe, Cr and C is produced:
› Pure chromium is obtained when chromite is heated strongly with Na2CO3

Then chromate is removed by dissolving in water, acidified to give the dichromate, then
precipitated and reduced with carbon

The Cr2O3 is reduced with Al

Uses
› Mo and W alloyed with steel make very hard alloys, which are used to make cutting
steel and machine tools.
› Molybdenum disulphide MoS2 is an excellent lubricant.
 Manganese Group
(Group 6 elements)

General properties
Oxidation state
› The electronic structure lor this group of elements is d5 s2, and suggests a maximum
oxidation state of (+VII).
› Manganese shows the widest range of oxidation states of all the elements, ranging
from (-III) to (+VII).
› The (+II) state is the most stable and common.
› Mn2+ ions exist in the solid, in solution and as complexes.
› However, in alkaline solution Mn2+ is readily oxidized to MnO2.
› The (+IV) state is found in the main ore pyrulsite MnO2.
› Mn(+VII) is well known as KMnO4, which is one of the strongest oxidizing agents
known in solution.
› Mn(+III) and Mn(+VI) tend to disproportionate, and the lower oxidation states exist
as carbonyl compounds or substituted carbonyl complexes.
› In contrast to the highly oxidizing properties of Mn (VII), the (+VII) state for Tc and
Re is the most common and stable, and shows only slight oxidizing properties.
 The (+VI) state tends to disproportionate and is not well known.

› The (+V) and (+IV) states for Tc and Re have an extensive chemistry.
› Re(III) is also stable and the halides form metal-metal bonds.
› The (+II) and lower oxidation states are uncommon and are strongly reducing.
› Thus, on descending the group there is an increase in stability of the highest oxidation
state and also a decrease in stability of the lower states.
 Size
› The atoms are smaller than those of the chromium group, and because of the lanthanide
contraction, the covalent and ionic radii of Tc and Re are almost identical.
 Consequently, these two elements have very similar properties, occur together,
and are very difficult to separate.

Extraction
› Manganese is the tenth most abundant element (1000 p.p.m.) in the earth's crust, where it
is found mainly as MnO2.
› Pure manganese is obtained by reducing MnO2 or Mn3O4 with Al (thermite reaction).
› There is little use for the pure metal, but in the steel industry, alloys are produced by
reducing mixtures of iron oxide and manganese oxide in a blast furnace.
› Technetium is obtained from spent uranium fuel rods from nuclear reactors, these are
oxidized, and the volatile Tc2O7 distilled out.
 Tc is a radioactive, metal that does not occur naturally (first man-made element).

› Rhenium occurs in small amounts in molybdenum ores and is recovered from the flue
dust from roasting molybdenum sulphide ores.

Uses
Uses Of Manganese:
› Manganese is used to produce a variety of important alloys and to deoxidize steel and
desulfurize.
› Manganese is an important additive to steel, because it removes both oxygen and
sulphur, and so improves the strength.
› It is also used in dry cell batteries.
› Manganese is used as a black-brown pigment in paint.
› It is an essential trace element for living creatures.
› It is mainly used to decolorize glass and to prepare violet-colored glass.
› Steel contains 1% manganese to increase strength and improve workability.
› Manganese steel has 13% manganese which is very strong and used for railway tracks,
rifle barrels, safes and prison bars.
› Drink cans are made from an alloy of aluminum that contains 1.5% manganese,
improving the resistance to corrosion.
› Manganese is also used as a catalyst, decolorize the glass that is colored green by iron
impurities.
› Manganese sulfate is used to make a fungicide.

Uses of Tc:
› The gamma-ray emitting technetium-99m (metastable) is widely used for medical
diagnostic studies.
 Several chemical forms are used to image different parts of the body.

› Technetium is a remarkable corrosion inhibitor for steel, and adding very small
amounts can provide excellent protection.
 This use is limited to closed systems as technetium is radioactive

Uses of Re:
› Re is used as an additive to tungsten- and molybdenum-based alloys to give useful
properties.
 These alloys are used for oven filaments and X-ray machines.
› Re catalysts are extremely resistant to poisoning.
› Re catalysts are used for the hydrogenation of fine chemicals.