INTRODUCTION TO TRANSITION

METALS
Dr F. Marais

TRANSITION ELEMENTS
All metals All have variable oxidation states Great industrial value due to increased density afforded by filling penultimate orbitals Size (volume occupied) doesnt increase much Mass increases across d- orbital more than it would normally moving down a period

Properties of d-block elements INTRODUCTION:

Transition & inner transition comprise 4 series
Sc(21) to Y(39) to Cu(29) Ag(47) Au(79) 3-d block 4-d block 4-f and 5-d block

La(57) to Ac(89) to

Lr(103)(lawrencium) 5-f and 6-d block

COMPLEX FORMATION

s- and p- block elements form only a few complexes.

Transition elements have small highly charged ions vacant low energy orbitals accept lone pairs of electrons form many complexes

Penultimate shell is expanding Many common properties All metallic Elements usually exist in more than one oxidation state

OXIDATION STATES AND ORDER OF FILLING OF D-BLOCK FOR 1ST SERIES

Sc Ti V Cr Mn Fe Co Ni Cu Zn

electronic structure

d1s2

d2s2

d3s2

d4s2 d5s1

d5s2

d6s2

d7s2

d8s2

d9s2 d10s1

d10s2

oxidation states

II III

II III IV

II III IV V

I II III IV V VI

II III IV V VI VII

II III IV V VI

II III IV V

II III IV

I II III

II

Reactivity decreases With each following series

From L to R across any series

*Pt, Au (& others in same groups) resist forming compounds with oxygen - referred to as noble metals.

The most stable states in the 1st series

when the d-shell is empty

when it is half full when it is completely full

PROPERTIES OF TRANSITION ELEMENTS

METALLIC

PROPERTIES

Metals

are dense and have high melting and boiling points. Since the electrons fill an inner orbital (from L to R) the atomic radius does not increase much so only density will increase across each series.

COLOURED IONS The d-orbital comprises 5 degenerate sub-orbitals which can each hold 2 electrons. Transitions of d-electrons is in the visible energy region. The colour of a particular transition metal ion depends upon: * The nature of ligands it is surrounded by * An incomplete d-level

Movement, or rearrangement, of electrons Within the 5 degenerate sets requires energy which is observed as visible colour. In addition, when electrons exist in degenerate sets The energy difference between the sets results in emission of energy. The degree of splitting between the levels depends on the type of ligand surrounding the metal ion. The different energy differences are observed as different wavelengths and for d-electrons, different colours within the visible spectrum.

CATALYTIC ACTIVITY Transition metal ions function as catalysts by changing their oxidation states. Catalysis at a solid surface involves formation of bonds between catalyst atoms and surface molecules.

In the transition elements both sand d- electrons are available This increases bonding possibilities lowers activation energy makes desired reaction more favourable.

PARAMAGNETISM
Most

substances are weakly repelled by a strong magnetic field = diamagnetic

Some

are weakly attracted by it = paramagnetic

large force of attraction is referred to as ferromagnetism.

Electrons spin on their axes within orbitals. A full orbital containing 2 electrons with opposite spin, (Hunds Rule) will have a zero magnetic moment. Increased levels of Para magnetism indicates maximum single occupation of orbitals.