FIRST ROW TRANSITION

METALS
• The characteristics of transition metals
• The electronic configuration of the first row transition elements and their ions
• The relatively small changes in atomic radii and ionization energies of the
elements across the periods
• The formation of colored ions by transition elements
 The Characteristics of Transition Metals
A transition element is a d-block element that forms one or more stable ions with an
incomplete d subshell.

PROPERTIES OF TRANSITION METALS

• They are strong, hard, shiny, malleable and ductile.
• They are good conductors of heat and electricity.
• They have a high density.
• They have a high melting and boiling point.
 VARYING OXIDATION STATES OF TRANSITION
METALS
The oxidation state is a positive or negative number which indicates the real or
theoretical number of electrons lost or gained by an element in a given compound.
• Transition metals have electrons in both 3d and 4s sublevels, and the similar
energies of these sublevels implies that electrons also have similar energies.
• As a result, it is easy for any transition element to form ions of roughly the same
stability by losing different numbers of electrons.
• Therefore, many transition elements exhibit more than one positive oxidation
number.
 DIAGRAM SHOWING OXIDATION STATES OF THE ELEMENTS
Sc to Zn
Sc Ti V Cr Mn Fe Co Ni Cu Zn

+3 +4 +5 +6 +7 +6 +5 +4 +3 +2

+3 +4 +5 +6 +5 +4 +3 +2

+2 +3 +4 +5 +4 +3 +2 +1

+1 +2 +3 +4 +3 +2 +1

+1 +2 +3 +2 +1

+1 +2 +1

+1
GENERALIZED STATEMENTS BASED
ON DIAGRAM
• All transition metals from titanium to copper exhibit oxidation numbers of +1, +2,
+3 in their compounds
• The common oxidation states for each elements include +2 and /or +3. The +3
states are more common at the beginning of the series while +2 states are common
towards the end.
• The highest oxidation states from Sc to Mn correspond to the respective numbers
of all the electrons outside the [Ar] core (3 for Sc, 4 for Ti,5 for V, 6 for Cr and 7
for Mn). After Mn, the increasing nuclear charge causes a greater pull on the d
electrons are relatively easier to remove , giving rise to the common oxidation state
of +2 in the elements from Fe to Zn.
GENERALIZED STATEMENTS BASED
ON DIAGRAM
• When transition metals form ions, they lose electrons from the 4s sublevel
before the 3d sublevel. This is because the 4s sublevel is lower in energy than
the 3d sublevel and is therefore more stable.
• V, which is [Ar] 3d3 4s2 forms the V3+ ion, [Ar] 3d2. The 4s electrons are
lost first, followed by one of the 3d electrons.
• Cr, which is [Ar] 3d5 4s1, forms the Cr3+ ion, [Ar] 3d3. To form the 3+ ion,
the 4s electron is lost first, followed by two of the 3d electrons.
 FORMATION OF COMPLEX IONS
Complex ions are ions that consist of a central metal ion bonded to anions or
neutral groups
• When a metal is a transition element, the ion is called a transition metal
complex ion.
• The anions and neutral groups are considered to be 'electron-rich', meaning
that they either possess a lone pair(s) or a negative charge.
• These are called ligands. Some examples include: H2O, NH3 and Cl-
• Only when the neutral group or anion is bonded to transition metal ions are
they considered ligands.
 FORMATION OF COMPLEX IONS
• In transition metal complexes, the ligand donates its lone pairs of electrons
to the vacant d orbitals on the transition metal ions to form dative covalent
bonds to the metal ions.
• The number of dative covalent bonds on the metal ion gives the
coordination number of the central ion. In the case of transition metals, the
most common coordination number is six, but four and two are not
uncommon.
 CATALYTIC PROPERTIES
A catalysts is a substance that alters (usually accelerates the rate of a chemical reaction
• Transition metals and their compounds catalyze reactions because they introduce a
totally new reaction pathway which has a lower activation energy of the catalyzed
reaction.
• Since the activation energy of the catalyzed reaction is lower, the reaction is faster.
• Transition metals and their compounds are important catalysts, both in biological
systems and in industry.
 CATALYTIC PROPERTIES
• Many transition metal ions of chromium, manganese, iron, cobalt, nickel and copper are
essential for the successful catalytic activity of various enzymes in humans, plants and
animals.
• These metal ions are required in very small amounts and as such, are referred to as trace
elements.
• For instance, cytochrome oxidase, one of the most important copper containing enzymes, is
involved when energy is obtained from the oxidation of food. If copper is absent, this
enzyme is completely inhibited and the organism is unable to metabolize food effectively.
• Some industrially important reactions in which transition metals ions function as catalysts
include: the Contact process, the Haber process and the hydrogenation of alkenes.
 THE CONTACT PROCESS
• In the manufacture of sulfuric acid, sulfur dioxide is oxidized to sulfur
trioxide by air at 4500C in the presence of a vanadium (V) oxide, V2O5,
catalyst:

2SO2 (g) + O2 (g) 2SO3 (g)

 THE HABER PROCESS
• Nitrogen and hydrogen combine under pressure at ~ 4500C in the presence
of a finely divided nickel catalyst:

N2 (g) + 3H2 (g) 2NH3 (g)

 HYDROGENATION OF ALKENES
• Liquid oils can be solidified into margarine by treatment with hydrogen at
2000C using a nickel catalyst. Hydrogen is added across some or all of the
double bonds.

RCH=CH2 + H2 RCH2CH3
 MANGNETIC PROPERTIES
Magnetic properties relate to the effects of exposure of a substance to an
external magnetic field.
o Magnetic properties which concern the attraction or repulsion of a substance
by a magnetic field arise principally from:
• The charge of the electrons;
• The spin angular momentum of the electrons, associated with the spin of
the electron about its axis
• The orbital angular momentum of the electrons, associated with the rotation
about the nucleus.
 MANGNETIC PROPERTIES
• The above factors are responsible for the existence of magnetic fields in an
atom
• Each of these internal magnetic fields interact with one another and with
external ones as well.
• A material can exhibit one of five distinct types of magnetism depending on
the way these magnetic fields interact with each other.
• However, only two types will be discussed in detail are paramagnetic and
diamagnetic.
 MANGNETIC PROPERTIES
Paramagnetic substances are substances which are attached to a magnetic field.

• Para magnetism is a property that occurs as a result of the presence of unpaired

electrons.
• Transition metals generally contain one or more unpaired electrons in the d
sublevel.
• Thus, most of the transition metals are paramagnetic.
• The paramagnetic character increases as the number of unpaired electrons increases.
 MANGNETIC PROPERTIES
Diamagnetic substances are those which are repelled by a magnetic field.

• The transition metals that contain paired electrons behave as diamagnetic

substances.
The Electronic Configuration of the First Row
Transition Elements and their Ions

• In atoms of the transition elements, the 4s subshell is normally filled and the rest of
the electrons occupy orbitals in the 3d subshell.
• However, chromium and copper atoms are the exceptions. Chromium atoms have
just one electron in the 4s subshell.
• The remaining five electrons are arranged in the 3d subshell so that each orbital is
occupied by one electron.
• Copper atoms also have just one electron in the 4s subshell. The remaining ten
electrons are arranged in the 3d subshell so that each orbital is filled by two
electrons.
The Electronic Configuration of the First Row
Transition Elements
 NOTE
• We do not define Sc and Zn as transition elements.
• Scandium forms only one ion (Sc3+) and this has no electrons in its 3d
subshell – the electronic configuration of Sc3+ is (Ar) 3d0 4s0.
• Zinc forms only one ion (Zn2+) and this has a complete 3d subshell – the
electronic configuration of Zn2+ is (Ar) 3d10 4s0
FIRST ROW TRANSITION ELEMENTS
AND THEIR IONS
• The transition elements are all metals. In common with all metals, their
atoms tend to lose electrons so they form positively charged ions.
• However, each transition metal can form more than one ion.
• For example, the common ions of copper are Cu+ and Cu2+.
• As a result, the transition metals have variable oxidation states.
• The resulting ions are often different colors.
FIRST ROW TRANSITION ELEMENTS
AND THEIR IONS
• Since transition metals form
multiple ions by losing electrons
from their 4s and 3d orbitals they
can form multiple compounds with
various oxidation states.
 DIAGRAM SHOWING THE MOST
COMMON OXIDATION STATES OF THE
FIRST ROW OF TRANSITION ELEMENTS
FIRST ROW TRANSITION ELEMENTS
AND THEIR IONS
• The existence of variable oxidation Examples of ions:
states means that the names of • V atom = 1s2 2s2 2p6 3s2 3p6 3d3 4s2
compounds containing transition
elements must have their oxidation • V3+ ion = 1s2 2s2 2p6 3s2 3p6 3d2 4s0
number included, e.g. manganese(IV)
oxide, cobalt(II) chloride. • Fe atom = 1s2 2s2 2p6 3s2 3p6 3d6 4s2
• When transition elements form ions, • Fe3+ ion = 1s2 2s2 2p6 3s2 3p6 3d5 4s0
their atoms lose electrons from the 4s
subshell first, followed by 3d electrons.
• Cu atom = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
• Cu2+ ion = 1s2 2s2 2p6 3s2 3p6 3d9 4s0
FIRST ROW TRANSITION ELEMENTS
AND THEIR IONS
• The most common oxidation state is • For example, vanadium’s maximum
+2, usually formed when the two 4s oxidation state is +5, involving its two
electrons are lost from the atoms. 4s electrons and its three 3d electrons.
• The maximum oxidation number of • At the end of the row, from iron
the transition elements at the start of onwards, the +2 oxidation state
the row involves all the 4s and 3d dominates as 3d electrons become
electrons in the atoms. increasingly harder to remove as the
nuclear charge increases across the
period.
FIRST ROW TRANSITION ELEMENTS
AND THEIR IONS
• The higher oxidation states of the transition elements are found in complex
ions or in compounds formed with oxygen or fluorine.
• Common examples are the chromate(VI) ion, CrO42–, and the
manganate(VII) ion, MnO4–.
 The Relatively Small Changes in Atomic Radii and
Ionization Energies of the Elements across the Periods
 The Relatively Small Changes in Atomic Radii and
Ionization Energies of the Elements across the Periods

Atomic radii is the distance from the center of the nucleus to the boundary of the surrounding shells of
electrons.
• As you begin to move across or down the periodic table, trends emerge that can help explain radii
change.
• The energy levels increase as you move down a group as the number of electrons increases. Each
subsequent energy level is further from the nucleus than the last. Therefore, the atomic radius
increases as the group and energy levels increase.
• Atomic radius decreases as you move across a period. As you go across a period electrons are added
to the same energy level. At the same time, protons are being added to the nucleus. The concentration
of more protons in the nucleus creates a ‘higher effective nuclear charge.’ In other words, there is a
stronger force of attraction pulling the electrons closer to the nucleus resulting in a smaller atomic
radius.
 The Relatively Small Changes in Atomic Radii and
Ionization Energies of the Elements across the Periods

Ionic radius is the distance between the nucleus and the electron in the
outermost shell of an ion.
• As you move down a column or group, the ionic radius increases. This is
because each row adds a new electron shell. Ionic radius decreases moving
from left to right across a row or period. More protons are added but the
outer valence shell remains the same so the positively charged nucleus in the
electrons more tightly. But, for the non-metallic elements, the ionic radius
increases because there are more electrons than protons.
 The Relatively Small Changes in Atomic Radii and
Ionization Energies of the Elements across the Periods

Ionization energy is the energy required to remove an electron from a neutral atom
in its gaseous phase.
• The lower this energy is, the more readily the atom becomes a cation. Therefore, the
higher this energy is, the more unlikely it is the atom becomes a cation. One atom is
a cation which is smaller in size and the other is an anion which is larger in size. So,
in order to account for the difference we must get the total distance between two
nuclei and divide the distance according to atomic size.
• The bigger the atomic size, the larger radius it will have.
 The Formation of Colored Ions by Transition
Elements
• The five d orbitals in an isolated transition metal atom or ion are described as
degenerate, meaning they are all at the same energy level.
The Formation of Colored Ions by Transition
Elements
 The Formation of Colored Ions by Transition
Elements
• In a complex with six ligands, the ligands are arranged in an octahedral shape
around the central metal ion.
• Th e lone pairs donated by the ligands into the transition metal ion repel electrons
in the two dx2–y2 and dz2 orbitals shown in the diagram above, more than those in the
other three d orbitals
• This is because these d orbitals line up with the co-ordinate bonds in the complex’s
octahedral shape and so they are closer to the bonding electrons in the octahedral
arrangement, increasing repulsion between electrons.
• Therefore the orbitals are split, with these two d orbitals at a slightly higher energy
level than the dyz, dxz and dxy orbitals.
 The Formation of Colored Ions by Transition
Elements
• In the presence of ligands a transition metal ion is not isolated. The co-
ordinate bonding from the ligands causes the five d orbitals in the transition
metal ion to split into two sets of non-degenerate orbitals at slightly different
energy levels
The Formation of Colored Ions by Transition
Elements
 The Formation of Colored Ions by Transition
Elements
• A Cu2+ ion has an electronic configuration of [Ar] 3d9. The figure above shows how
the nine d electrons are distributed between the non-degenerate orbitals formed in a
complex with ligands.
• The difference in the energy between the non-degenerate d orbitals is labelled ΔE.
• ΔE is part of the visible spectrum of light. So, when light shines on the solution
containing the Cu(H2O)62+ complex, an electron absorbs this amount of energy. It
uses this energy to jump into the higher of the two non-degenerate energy levels.
 EXPLAINING THE FORMATION OF
COLOURED IONS

• In copper complexes, the rest of the visible spectrum that passes through the
solution makes it appear blue in color.
• The exact energy difference (ΔE) between the nondegenerate d orbitals in a
transition metal ion is affected by many factors.
• One of these factors is the identity of the ligands that surround the
transition metal ion.
• As you have seen, a solution containing Cu(H2O)62+ is a light blue, whereas a
solution containing Cu(NH3)2(H2O)22+ is a very deep shade of blue.
 EXPLAINING THE FORMATION OF
COLOURED IONS

• The color change arises because the presence of the ammonia ligands causes
the d orbitals to split by a different amount of energy.
• This means that the size of ΔE changes and this results in a slightly different
amount of energy being absorbed by electrons jumping up to the higher
orbitals.
• Therefore a different color is absorbed from visible light, so a different color
is seen.
EXPERIMENT EXPLAINING THE FORMATION
OF COLOURED IONS