CHM 221: Inorganic Chemistry I

2nd Semester 2021/2022

Lecture Note
Course Outline
• Systematic chemistry of the representative elements of group I-VIII
• Periodic trends
• General properties of transition elements
• Concepts of acids and bases: Arrhenius, Bronsted-Lowry and Lewis concepts

Transition Elements

Introduction
In the extended form of the periodic table, the elements have been grouped into four
blocks namely s, p, d and f-blocks. The elements belonging to groups 3 to 12 are
called d-block or transition elements, and are present between s-block and p-block
elements These elements are called transition elements because their properties are
intermediate between the properties of s-block and p-block elements i.e. d-block
elements represent a transition in properties from electropositive s-block elements to
least electropositive p-block elements. The transition elements either have partially
filled d-orbital (or f-orbital) thus, their outermost-shells are incomplete
Forty elements belong to d-block with the fourth, fifth, sixth and seventh periods
consisting of ten elements each. There are four complete rows (called series) of ten
elements each i.e., first transition to fourth transition series. Each series starts with a
member of group three (IIIB) and ends with a member of group twelve (IIB) as shown
below.

The d-block elements include the most common metal used in construction and
manufacturing (iron), metals that are valued for their beauty (gold, silver and platinum),
metals used in coins (nickel, copper) and metals used in modern technology (titanium).
Copper, silver, gold and iron were known and used in early civilization. Certain d-block
elements are also important in living organisms. In this course we shall focus on the
d-block elements, specifically elements of the first transition series.
Exercise: Discuss the applications of d-block elements

Electronic Configuration

Page 1 of 9
In the d-block transition elements, the last differentiating electron is accommodated on
penultimate d-orbitals, i.e., d-orbitals are successively filled. The first transition series
consist of ten elements i.e., from Scandium (Z=21) to Zinc (Z=30). These are also
called 1st row transition elements. Their electronic configurations are given in table
below:

Table 1.0 Electronic Configuration of 1st Row Transition Elements (Z = atomic

number)

Some general trends in the electronic configuration of 1st row transition elements
include the following:
(i) The 4s orbitals are conventionally denoted as the outermost orbitals even
though in the atoms of these elements the 3d and 4s orbitals have similar
energies. This is because radial probability studies have shown that their 4s
electrons are positioned furthermost from the nucleus. Thus, their neutral
atoms lose a 4s electron first before 3d electrons.
(ii) Along the 1st row transition series, the 3d shell is gradually filled up except
for chromium (3d54s1) and copper (3d104s1) which have configurations that
are different than expected. This is explained on the basis of stability
concept of half-filled or completely filled d-orbitals. The d-subshell is more
stable when 5 or 10 electrons are present, i.e., every d-orbital is either singly
occupied or doubly occupied.

(iii) Copper is included amongst the transition elements even though its outer
electronic configuration is 3d104s1. This is because it has the 3d 9
configuration in its commonly occurring +2 oxidation state. i.e Cu2+ ions.
(iv) Zinc is not commonly considered a transition element since in both the
element and its compound, the 3d electron shell remains fully filled. It
therefore does not show some of the characteristic properties of transition
Page 2 of 9
 elements However, zinc metals showing similarities in some of chemical
properties with transition metals are also included in this block. These are
considered as end members of the transition series in order to maintain a
rational classification of elements.
(v) Scandium is included amongst the transition elements only by definition. So
far, only the +3-oxidation state of Sc has been established. Its compounds
therefore do not show the general characteristics of transition elements.

General Characteristics of Transition Elements

The members belonging to a given transition series do not differ so much from one
another. These elements show horizontal and vertical relationships or they show
similarities in a period as well as in group. The general trends of some of the important
properties are discussed below.

1. Metallic Character
All the 1st row transition elements are metals. They exhibit most of the properties of
metals. They possess metallic lustre, high density, high melting and boiling points,
malleability, ductility, high tensile strength, hardness, brittleness, etc. They are good
conductors of heat and electricity. They also exhibit all the three types of structures
which are characteristics of metals i.e., face centred cubic (fcc), hexagonal closed
packed (hcp) and body centred cubic (bcc).
These properties reveal that both metallic and covalent bonding are present in the
atoms of this element. The metallic bonding is due to possession of one or two
electrons in the outermost energy shell and relatively low ionisation energies. Copper
shows exceptionally high thermal and electrical conductivity because of the existence
of metallic bonds.
Their brittleness are associated with covalent bonding, while their hardness is due to
the presence of strong metallic bonding among their atoms. This is formed from
overlap between the singly filled orbitals of different atoms of the elements. The
greater the number of unpaired electrons, the greater the number of metallic bonds
and, therefore the greater the hardness of the metals. Cr for example has maximum
number of unpaired electrons and is a very hard metal. Zn is softer in nature since it
does not have any unpaired d-orbital electron.

2. Atomic/Ionic Radii
The atomic radii of the elements of the 1st row transition elements decrease with
increase in atomic number but this decrease becomes small after midway. Thus, the
atomic radius gradually decreases from scandium to chromium but from chromium to
copper, it is nearly the same. As shown below

Table 1.1 Atomic radii (pm) of 1st row transition elements

The decrease in atomic radii in the 1st transition series, in the beginning, is due to an
increase in nuclear charge from member to member which tends to pull the ns
electrons inward, i.e., it tends to reduce the size. At the same time, the addition of

Page 3 of 9
extra electrons to d-orbitals also provides the screening effect. As the number of d
electrons increases, the screening effect increases. Thus, there are operating two
effects namely screening effect and nuclear charge effect which oppose each other.
In the midway onwards of the series both these effects become nearly equal and thus,
there is no change in atomic radii (i.e. for Mn and Fe)
The values of atomic radii at the end of the series are bit higher. This is due to electron-
electron repulsions d-orbital electrons. These repulsions become predominant at the
end of the series and thus size increases. It is evident from the high atomic radii value
of zinc.
The ionic radii follow the same trend as the atomic radii. For the same oxidation state,
the ionic radii generally decrease as the atomic number increases.

The ionic radii also decrease with increase of charge on the ion.

.
3. Melting and Boiling Points.
The transition metals have very high melting and boiling points. In each series, the
melting points of these metals rise to a maximum value and then decrease with
increase in atomic number. However, manganese has abnormally low melting points.
The melting points of most of the first transition series elements except Zn above
900ºC.The high melting and boiling points of transition metals are attributed to the
stronger forces that bind their atom together. The presence of one or more unpaired
d-electrons contributes to higher interatomic forces on account of covalent bonding
and therefore, to high melting points. However, this concept does not explain why
manganese having five unpaired d electrons possesses lower melting point than that
of vanadium or cobalt which have only three unpaired d electrons. The complex
structure is responsible for this abnormal behaviour. When no unpaired electrons are
present, the melting points is low as in the case of Zn.

4. Ionisation energies
There is a gradual but irregular increase in the ionisation energy values as we move
from left to right along the first transition series elements. The increase in nuclear
charge as we move across the row would attract the outermost electrons with greater
force and hence the ionisation energies are expected to increase at each step.
However, since the differentiating electron is added to the 3d orbitals, it screens the
4s electrons thereby decreasing the attraction between the nucleus and the 4s
electrons. This screening effect decreases the magnitude of the nuclear charge and
consequently, the ionisation energies increase but quite slowly along the first row. As
shown in the vales (in kj mol-1) below.

Page 4 of 9
5. Variable oxidation states
The transition elements with the exception of a few show a large number of oxidation
state. The various oxidation states are related to the electronic configuration of their
atoms. Variable oxidation states of the first row transition elements is due to the
involvement of d-orbital and s-orbital electrons in bonding as the energies of both
subshells are nearly equal. The lower oxidation state is generally shown when s-orbital
electrons participate in bonding, while higher oxidation states are exhibited when d-
orbital and s-orbital electron take part in bonding. For example, Fe could lose its two
4s electron to form Fe2+ ion or lose its 4s electrons and one 3d electron to form Fe 3+
ions. Thereby existing in the +2 and +3 oxidation states. Amongst the 1st row transition
elements, manganese has the widest range of oxidation states (from -1 to +7).
The oxidation states of first row transition elements are tabulated below. The oxidation
states within the brackets are not stable.

Trends in Oxidation States of 1st Row Transition Metals

The following trends can be observed amongst the 1st row transition metals:
(i) Generally, within the transition series, the highest oxidation state increases with
increase of atomic number, reaching to a maximum in the middle and then starts
decreasing. For example, in the first transition series manganese shows the maximum
oxidation state of +7.
(ii) In general, the minimum oxidation state sown by a transition metal is equal to
the number of ns-electrons. Except scandium, (which has +3 oxidation state), there is
a common occurrence of +2 oxidation state where the 4s electrons have been formally
lost. For chromium and copper, the lowest oxidation state is +1.
(iii) In the first five elements of the first transition series, the maximum oxidation
state is equal to the sum of the 4s and 3d-electrons. For example, maximum oxidation

Page 5 of 9
state for titanium is +4 for vanadium +5. For the remaining five elements the maximum
oxidation state is not related to their electronic configurations. The common oxidation
states for the elements from Fe to Ni are +2 or +3. The oxidation state higher than +3
is rarely shown.
(iv) Some of the transition metals form compounds in zero oxidation state. The
common examples are Ni(CO)4 and Fe(CO)5 in which nickel and iron are in zerovalent
state.
(v) In +2 and +3 oxidation states, the bonds formed are mostly ionic. On the other
hand, in higher oxidation states, the bonds formed are essentially covalent. Higher
states are usually attained with elements of high electronegativity such as fluorine and
oxygen. For example, in ions such as MnO4- the bond formed is covalent.
(vi) The relative stability of various oxidation states of a given element can be
explained on the basis of stability of d 0, d5 and d10 configurations. For example, Ti4+
(3d04s0) is more stable than Ti3+(3d34s0). Mn2+ is also more stable than Mn3+.
6. Tendency to form Coloured Complex Ions
A substance appears coloured because it absorbs light at-specific wavelengths in the
visible part of the electromagnetic spectrum and transmits or reflects the rest of the
wavelengths. Each wavelength of visible light represents a different colour, while white
light is a combination of all colours. Most of the compounds of transition metals are
coloured in the solid or in solution states. The colour of transition metal ions arises
from the excitation of electrons from the d-orbitals of lower energy to the d-orbitals of
higher energy. The energy required for d--d electron excitations is available in the
visible range. It is for this reason that transition metal ions have the property to absorb
certain radiations from the visible region and exhibit the complementary colour.
The transition metal ions which have completely filled d-orbitals such as Zn2+ ions are
colourless as the excitation of electron or electrons is not possible within d-orbitals.
The transition metal ions which have completely empty d-orbitals such as Sc3+ are
also colourless. The colours and outer electronic configurations of important ions of
the elements of first transition series are tabulated below:
Table 1.2: colours and magnetic moments of ions of the first transition series

Page 6 of 9
7. Magnetic properties
Majority of substances show magnetic nature. These are either paramagnetic or
diamagnetic. A paramagnetic substance is one which is weakly attracted into a
magnetic field and a diamagnetic substance is one which is repelled by a magnetic
field. The paramagnetic behaviour arises due to the presence of one or more singly
occupied atomic orbitals, while diamagnetic behaviour is due to presence of paired
electrons in the atomic orbitals.
Most of the compounds of transition elements are paramagnetic in nature as unpaired
electrons in d-subshell are present. The magnetic character is expressed in terms of
magnetic moment. Paramagnetic behaviour increases as the number of unpaired
electrons increases from 1 to 5. After d5 configuration, there is decrease in magnetic
moment as the number of unpaired electrons decreases. In the case of iron, cobalt
and nickel the unpaired electron spins are much more pronounced. As a result, these
elements are much more paramagnetic than the rest of the elements. These elements
are termed ferromagnetic and can be magnetised.

8. Tendency to form Complexes

1st row transition metals or d-block elements have a marked ability to form complex
compounds. This ability is on account of following three reasons:
(i) Small size (ii) high nuclear charge (iii) a number of vacant orbitals of equivalent
energy where the electrons donated by ligands can be accommodated.
Ligands are species with lone pair of electrons which they can readily donate. These
species can be neutral molecules such as NH3, H2O, NO, etc., or ions such as Cl- CN-
, etc. The number of attachments with ligands are usually either four or six, i.e., the
coordination number of metal ion is usually four or six. The compounds containing
complex ions are termed as coordination compounds. [Cu(NH3)4Cl2] and Ni(CO)4 are
some examples of coordination compounds.

9. Catalytic properties
Most transition metals and their compounds act as catalyst. Their catalytic activity can
be attributed to their ability to exhibit variable oxidation states. Catalysis on the surface
involves formation of bonds between reactant molecules and the surface of the
Page 7 of 9
catalyst atoms. Since transition metals can use both their 4s and 3d electrons for bond
formation, this has the effect of increasing the concentration of the reactant at the
catalyst surface and weakening the bonds in the reactant molecule. This results in
lowering of activation energy and subsequently speeding up of the rate of reaction.
Some common examples are (i) Pt - used as a catalyst in the manufacture of H2S04.
(ii) Fe - used as a catalyst in the manufacture of NH 3 by Haber process (iii) Ni.- used
as a catalyst in the hydrogenation of oils.

10. Alloy Formation

Transition metals form a large number of alloys. Since d-block elements are quite
similar in atomic size, the atoms of one metal can substitute the atoms of other metal
in its crystal lattice. Thus, on cooling a mixture solution of two or more transition metals,
smooth solid alloys are formed. Alloys containing mercury as one of the constituent
elements are called amalgams. The purpose of making alloys is to develop some
useful properties which are absent in the constituent elements. For example: stainless
steel is a corrosion-resistant alloy of iron, chromium and in some cases, nickel and
other metals.

11. Formation of Interstitial Compounds

Small non-metallic atoms such as H, B, C, N, etc., are able to occupy interstitial spaces
of the lattices of the d-block elements to form combinations which are termed
interstitial compounds. These are non-stoichiometric in nature and do not follow the
common rules of valency. The bonds present are neither typically ionic nor covalent.
The formulae do not correspond to any normal oxidation state of the metal. Some of
the characteristics of interstitial compounds are:
(i) The interstitial compounds have similar chemical properties as the parent metals
but differ appreciably in their physical properties such as density, conductivity,
(ii) As a result of filling up of the interstitial spaces, the metals become rigid and hard.
Steel is quite hard as it is interstitial compound of Fe and C.
(iii) Interstitial compounds possess high melting points which are higher than those of
pure metals.

Some Important Compounds of Transition metals

The transition metals combine with a number of non-metals such as oxygen, nitrogen,
carbon, halogens, sulphur and phosphorus, etc., to form useful binary compounds.
General trends in oxides, halides and sulphides are discussed below.
(a) Oxides: The elements of first transition series form a number of oxides having
general formulae MO, M2O3, M3O4. The oxides are generally formed when the metals
are strongly heated at high temperature in the atmosphere of oxygen. These oxides
exhibit acidic, basic and amphoteric behaviour. The oxides in lower oxidation states
are basic in nature, the oxides in intermediate oxidation states are amphoteric while
the oxides of higher oxidation states are acidic in nature. The important and common
oxides of the elements of first transition series include TiO, V2O3 etc.
(b) Halides: Transition metals combine with halogens at high temperatures to form
compounds called halides. On account of high activation energies of these reactions,
high temperature is usually needed to start the reaction, but once the reaction starts,

Page 8 of 9
the heat of reaction is sufficient to maintain the continuity of the reaction (Reactions
are exothermic in nature). Metals in higher oxidation states only form fluorides as it is
the most electronegative and reactive element.
(c) Sulphides: Sulphides of transition metals can be formed either by direct
combination of the metals with sulphur or by action of H 2S or Na2S on the salts of
these metals. Sulphides of transition metals are coloured usually black and are
insoluble in water.

Page 9 of 9