CHE 410: TRANSITION

METAL CHEMISTRY

Course instructor: Dr D.A. Ondigo

 Introduction
• A transition element is defined as the one which has
incomplete d orbitals/ partially filled (n-1) d orbital either
in its ground state or in any one of its oxidation states.
• d-block elements: elements last electron enters in d sub
shell or d orbital.
• Elements of periodic table belonging to group 3 to 12 are
known as d-block elements.
• The d -block elements lies in between s- and p-block
elements in the long form of periodic table
• What is the difference between d - Block Elements &
Transition elements?
• All d block elements are not transition elements but all
transition elements are d-block elements
 Introduction Cont…
• All d block elements are not transition elements because d block
elements like Zinc have full d10 configuration in their ground
state as well as in their common oxidation state.
• This is not according to definition of transition elements.
• There are three complete series (from period 4-6 in the group 3-
12) of the transition elements.
3d series (4th period) : Scandium (21SC) to Zinc (30Zn)
4d series (5th period) : Yttrium (39Y) to Cadmium (48Cd)
5d series (6th period) : Lanthanum (57La) to Mercury (80Hg) except 58Ce
to 71Lu
• The general outer most electronic configuration of d-block
elements is (n − 1)d1 − 10 ns1−2, where n = outermost shell.
• The following tables describes the outer shell electronic
configurations of transition elements in ground state:
 Table: Outer Electronic Configurations of the Transition Elements (ground state)

1st Series

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Z 21 22 23 24 25 26 27 28 29 30
4s 2 2 2 1 2 2 2 2 1 2
3d 1 2 3 5 5 6 7 8 10 10

2nd Series
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
5s 2 2 1 1 1 1 1 0 1 2
4d 1 2 4 5 6 7 8 10 10 10
 Table Cont…
3rd Series
La Hf Ta W Re Os Ir Pt Au Hg
Z 57 72 73 74 75 76 77 78 79 80
6s 2 2 2 2 2 2 2 1 1 2
5d 1 2 3 4 5 6 7 9 10 10

•The electronic configurations of Zn, Cd and Hg are

represented by general formula (n- 1)d10 ns2. 
•They have completely filled d-orbitals in ground state as
well as in their common oxidation states, hence are not
considered as transition elements.
 Introduction Cont…
• On the other hand, silver (47Ag) has also completely filled d-orbitals
in ground state, but in +2 oxidation state it has 4 d9 configuration
which is incomplete, thus silver is considered to be transition element.
QUIZ………
Which of the d-block elements may not be regarded as the
transition elements?
 Zn, Cd and Hg
Why Zn, Cd and Hg are not considered as transition elements.
 Because they do not have vacant d-orbitals neither in the atomic
state or in any stable oxidation state.
Why Scandium is a transition element but Zinc is not.
Scandium is a transition because it has incompletely filled d orbitals
in its ground state but Zinc have full d10 configuration in their
ground state as well as in their common oxidation state
 QUIZ Cont….
Copper atom has completely filled d orbital (3d10) in its ground
state, yet it is transition element. Why
Copper (Z = 29) can exhibit +2 oxidation state wherein it will
have incompletely filled d-orbitals (3d), hence a transition
element.
Silver atom has completely filled d orbital (4d10) in its ground
state, yet it is transition element. Why
Silver (Z = 47) can exhibit +2 oxidation state wherein it will have
incompletely filled d-orbitals (4d), hence a transition element.
Why the very name ‘transition’ given to the elements of d-block.
The very name ‘transition’ given to the elements of d-block is
only because of their position between s– and p– block elements.
 General characteristics of transition elements

• The transition metals show almost similar physical and chemical properties
due to similar outer electronic configuration.
• However, they differ in some properties due to difference in number of
electrons in their d-orbitals.
(i) Metallic character: 
• Transition elements are malleable and ductile metals having metallic
luster/shine.
• These are good conductors of heat and electricity.
• Except mercury (a liquid) all are solid.
(ii) Atomic volume and density : 
• They have lower atomic volume than those of the elements of s and
p-blocks.
Reason:
Their increased nuclear charge is poorly screened and so attracts all the
electrons more strongly.
 General characteristics Cont….

In addition, the added electrons occupy the inner d-orbitals.

• Density is inversely proportional to volumes hence, they have high
densities (>5 gcm-3 except Sc 3.0 gcm-3 and Y (Yttrium) and Ti with 4.5
gcm-3).
• The densities increase both across the period and down the groups.
(iii) Melting and boiling points: 
• Melting points and boiling points are directly related to the strength of
metallic bonds which in turn depends on the number of unpaired electrons.
• It rises to the maximum and then decreases in a period.
• They generally increase down a group due to the stronger metallic bonds
due to better overlap resulting from larger atomic orbitals down each
group.
• Partially filled especially half filled d-orbitals form additional covalent
bonding due to overlapping of d-sub shells of adjacent atoms resulting high
MP and BP and also hard and brittle nature.
 General characteristics Cont….
(iv) Atomic radii: 
• Atomic radii of transition elements in a period are smaller
than s-block elements and larger than p-block elements.
• In a period atomic radii decreases initially and varies irregularly
showing near constancy till 11th group and then increases in the
12th group with increasing atomic number.
• Nuclear charge and also the shielding effect of electrons
increase and counter balance the effects resulting small decrease
in atomic radii.
• But in Zn, Cd and Hg there is increase in atomic radii due to
electron repulsion which exceeds the attraction between nucleus
and the electrons of outer most orbital.
• The atomic radii of 5th period elements are greater than that of
the 4th period elements due to increase in the number of orbitals.
 General characteristics Cont….

• But 5th and 6th period elements have nearly the same radii due to the
lanthanide contraction.
Lanthanide contraction;
• In multi-electron atoms, the decrease in radius brought about by an
increase in nuclear charge is partially offset by increasing
electrostatic repulsion among electrons.
• As electrons are added in outer shells, electrons already present shield the
outer electrons from nuclear charge, making them experience a lower
effective nuclear charge.
• The 4f-electrons are the poorest at shielding the outer electrons from the
nucleus.
• The shielding effect exerted by the inner electrons decreases in the
order s > p > d > f.
• Usually, as a particular sub-shell is filled in a period, atomic radii
decreases.
 General characteristics Cont….
• This effect is particularly pronounced in the case of the lanthanides,
as their 4f sub-shells are being filled across the period, they are less
and less able to shield the outer (5th and 6th) shell electrons.
• Thus the shielding effect is less able to counter the decrease in radius
caused by increasing nuclear charge.
Ionic Radii:
• Ionic radii decrease from left to right with increase in oxidation state.
• Since the metals exhibit variable oxidation states; for each element,
ionic radii decreases with increasing oxidation state e.g. Ti2+ > Ti3+ >
Ti4+.
(v) Ionization energy: 
• Ionization energies of transition metals are generally very high.
• Because of the irregular variation of atomic size, they show very
little and irregular variation in their ionization energies.
 Table: 1st IEs of TEs in KJ/mol

Sc Ti V Cr Mn Fe Co Ni Cu Zn
633.1 658.8 650.9 652.9 717.3 762.5 760.4 737.1 745.5 906.4
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
600 640.1 652.1 684.3 702 710.2 719.7 804.4 731.0 867.8
La Hf Ta W Re Os Ir Pt Au Hg
538.1 658.5 761 770 760 840 880 870 890.1 1007

• Notice from the table that across any period, the values
of the 1st IEs increases gradually even though the
increase in not very regular.
 General characteristics Cont….
Explanation;
• When we move from left to right in a given series, nuclear
charge and hence effective nuclear charge increases.
• The increased nuclear charge would attract the ns 2 electron
cloud with greater force and hence the IEs are expected to
increase in each step.
• However, as the electron is added to the (n-1)d sub shell at each
next element, the ns2 electrons are shielded more and more.
• The effect of the increasing nuclear charge is opposed to the
additional screening effect of the nucleus and consequently, the
IEs increase but quite slowly i.e.
Between Mn and Cu there is a slight decrease.
This is due to the buildup of electrons immediately underlying (n-1)
sub-shells that efficiently shields the 4s electrons from the nucleus thus
minimizing the increase in effective nuclear charge from one element
to another.
 General characteristics Cont….
• Zn, Cd and Hg have the highest IE in their respective periods
due to the extra stability associated with their completely
filled orbitals (write their electronic configurations).
• Down the groups, the trend is not regular.
• Between the 1st and 2ndperiod elements the expected decrease
in 1st IEs is observed.
• This is attributed to the increase in atomic sizes and reduction
in effective nuclear charges.
• In the elements following La, the IE increases instead of
decreasing.
• These elements have smaller than expected atomic radii due
to lanthanide contraction.
• The valence electrons in these elements experience higher
than expected effective nuclear charges because they come
after 4f sub-shell which shields the nucleus ineffectively.
 General characteristics Cont….
• The IE increases across a period due to decrease in size.
• Zn has the highest IE due to fully filled orbitals though
the size is larger.
• IE3 > IE2 > IE1; due to increasing positive charge on them.
• IE2 of V < Cr > Mn and Ni < Cu > Zn
• IE3 of Mn is much higher than that of Fe due to its
electronic configuration.  
• IE1 of 5d series is much higher than those of 4 d and
3d due to weak shielding of 4f electrons.
Questions;
Explain how the 1st IE is related to the;
(i) Metallic character of an element
(ii)Stability of a compound/oxidation state; i.e. would you
expect K2[PtCl6] to be more or less stable than K2[NiCl6].
 General characteristics Cont….
(vi) Oxidation states: 
• All TEs except first and last number of the series exhibit
variable oxidation states because (n - 1)d and ns have
comparable energies so that both can enter into chemical bond
formation.
• The maximum oxidation state shown by first series increases
from Sc to Mn and then decreases.
• The common oxidation state of first series is +3 (except Sc).
• The highest oxidation state of transition elements is 8 (Os and
Ru).
• The compounds of transition elements in lower oxidation
states +2 and +3 are mostly ionic and of higher states are
covalent e.g., ZnCl2 and CdCl2 are ionic, higher oxidation
state of transition elements are shown in oxides and
oxoacids (e.g., vanadate (VO42-), chromate (CrO42-).
 General characteristics Cont….
• Transition metals with fluorine and oxygen exhibit higher
oxidation state due to higher electronegative nature of
fluorine and oxygen.
• Transition metals also exhibit +1 and 0 oxidation states e.g.;
Cu2Cl2, AgCl, Hg2Cl2 (oxidation states of the metal is +1)
Ni(CO)4, Fe(CO)5(O.S. of metal is 0)
• When the metals exhibit more than one oxidation states
their relative stabilities can be known from their standard
electrode potential e.g.,
Lower standard reduction potential Cu2+ indicates that Cu2+ is
more stable than Cu+ in aqueous medium.
(vii) Standard electrode potential: 
• Electrode potential is the electric potential developed on a
metal electrode when it is in equilibrium with a solution
of its ions, taking electrons from the electrode.
 General characteristics Cont….
• There is irregular variation in electrode potential due to
irregular variation in ionization enthalpy, sublimation energy
and energy of hydration.
• The E° value decreases from left to right across a period; Mn,
Ni and Zn have higher values than expected because of their
half-filled or completely filled 3d-orbitals in case of Mn2+
and Zn2+and the highest negative enthalpy of hydration Ni2+.
(viii) Reducing properties: 
• The electrode (oxidation) potentials of the first transition
series metals (except Cu) are quite high.
• Hence, they are expected to be oxidized easily to their ions.
• They should be good reducing agents but they are not so
because of their high heat of vaporization, high ionization
potentials and low heat of hydration.
 General characteristics Cont….

• Since the oxidation potential of Cu (-0.34 V) is negative, it

has a low tendency to change to Cu+2 ions and does not
displace H+ ions from acid solutions.
(ix) Magnetic properties: 
• A diamagnetic substance is one in which all the electrons are
paired while the substances containing unpaired electrons are
said to be paramagnetic.
• Except the ions of d0 (Sc+3, Ti+4) or d10 (Cu+,
Zn+2) configurations, all other simple ions of transition
elements contain unpaired electrons in their (n-1)d sub-shell
and are therefore, paramagnetic.
• The magnetic moments (μ) of the elements of first transition
series can be calculated with the unpaired electrons (n) by
the spin only formula.
μ = √n(n + 2) BM (Bohr Magneton)
 General characteristics Cont….
(x) Complex formation:
• The tendency to form complex ions is due to:
The high charge on the transition metal ions and
The availability of d-orbitals for accommodating electrons
donated by the ligands.
(xi) Catalytic property: 
• Most of the transition metals and their compounds
possess catalytic properties. the catalytic activity of
transition metal ions is attributed to the following two
reasons:
Variable oxidation states due to which they can form a variety
of unstable intermediate products.
Large surface area so that the reactants are adsorbed on the
surface and come closer to each other facilitating the reaction
process.
 General characteristics Cont….

(xii) Color: 
• Most of the transition metal ions in solution as well as in
solid states are colored.
• This is due to the partial absorption of visible light.
• The absorbed light promotes the electron from one orbital
to another orbital of the same d sub-shell.
• Since the electronic transition occurs within the d-orbitals of
the transition metal ions, they are called d–d transitions.
(xiii) Alloy formation: 
• Most of the transition metals form alloys because of their
similar radii, transition metals can mutually substitute their
positions in their crystal lattices.
(xiv) Interstitial compounds: 
• Interstitial compounds are those in which small atoms
occupy the interstitial sites in the crystal lattice.
 General characteristics Cont….
• Interstitial compounds are well known for transition metals because
small-sized atoms of H, B, C, N,  etc. can easily occupy positions in
the voids present in the crystal lattices of transition metals.
(xv) Reactivity: 
• Though the transition elements are sufficiently electropositive, they
are not very reactive because of:
Their high heats of sublimation and
Their high ionization energies
(xvi) Oxides: 
• Transition metals form oxides of the general composition MO,
M2O3, MO2, M2O5 and MO6.
• Oxides in the lower oxidation states are generally basic in
nature and those in the higher oxidation states are amphoteric
or acidic in nature e.g.
V2O2 V2 O4 V 2O 5
Less basic more basic amphoteric
END OF LECTURE