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TRANSITION METAL
CHEMISTRY
4f
DISTANCE FROM NUCLEUS
4d
INCREASING ENERGY /
4
4p
3d
4s
3 3p
KNOCKHARDY PUBLISHING
2015
SPECIFICATIONS
KNOCKHARDY PUBLISHING
TRANSITION METALS
INTRODUCTION
This Powerpoint show is one of several produced to help students
understand selected topics at AS and A2 level Chemistry. It is based on the
requirements of the AQA and OCR specifications but is suitable for other
examination boards.
Individual students may use the material at home for revision purposes or it
may be used for classroom teaching if an interactive white board is
available.
Accompanying notes on this, and the full range of AS and A2 topics, are
available from the KNOCKHARDY SCIENCE WEBSITE at...
www.knockhardy.org.uk/sci.htm
CONTENTS
• Definition
• Metallic properties
• Electronic configurations
• Variable oxidation state
• Coloured ions
• Complex ion formation
• Shapes of complexes
• Isomerism in complexes
• Catalytic properties
TRANSITION METALS
The first row runs from scandium to zinc filling the 3d orbitals.
The first row runs from scandium to zinc filling the 3d orbitals.
Metallic
properties all the transition elements are metals
strong metallic bonds due to small ionic size and close packing
higher melting, boiling points and densities than s-block metals
K Ca Sc Ti V Cr Mn Fe Co
density /
g cm-3 0.86 1.55 3 4.5 6.1 7.2 7.4 7.9 8.9
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
POTASSIUM
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
‘Aufbau’
1s2 2s2 2p6 3s2 3p6 4s1 Principle
CALCIUM
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
SCANDIUM
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
With the lower energy 4s orbital filled, the next electrons can now fill p the 3d
orbitals. There are five d orbitals. They are filled according to Hund’s Rule.
BUT WATCH OUT FOR TWO SPECIAL CASES.
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
TITANIUM
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
The 3d orbitals are filled according to Hund’s rule so the next electron doesn’t pair
up but goes into an empty orbital in the same sub level.
HUND’S RULE OF
MAXIMUM MULTIPLICITY
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
VANADIUM
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
The 3d orbitals are filled according to Hund’s rule so the next electron doesn’t pair
up but goes into an empty orbital in the same sub level.
HUND’S RULE OF
MAXIMUM MULTIPLICITY
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
CHROMIUM
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
MANGANESE
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
The new electron goes into the 4s to restore its filled state.
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
IRON
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
Orbitals are filled according to Hund’s Rule. They continue to pair up.
HUND’S RULE OF
MAXIMUM MULTIPLICITY
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
COBALT
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
Orbitals are filled according to Hund’s Rule. They continue to pair up.
HUND’S RULE OF
MAXIMUM MULTIPLICITY
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
NICKEL
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
Orbitals are filled according to Hund’s Rule. They continue to pair up.
HUND’S RULE OF
MAXIMUM MULTIPLICITY
ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS
COPPER
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
ZINC
4f
4d
INCREASING ENERGY /
4
DISTANCE FROM
4p
NUCLEUS
3d
4s
3 3p
The electron goes into the 4s to restore its filled state and complete the 3d and 4s
orbital filling.
ELECTRONIC CONFIGURATIONS
When electrons are removed they come from the 4s orbitals first
Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1 Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2
Cu+ 1s2 2s2 2p6 3s2 3p6 3d10 Ti2+ 1s2 2s2 2p6 3s2 3p6 3d2
Cu2+ 1s2 2s2 2p6 3s2 3p6 3d9 Ti3+ 1s2 2s 2p6 3s2 3p6 3d1
Ti4+ 1s2 2s2 2p6 3s2 3p6
COLOURED IONS
A characteristic of transition metals is their ability to form coloured compounds
xy xz yz
x2-y2 z2
SPLITTING OF 3d ORBITALS
Placing ligands around a central ion causes the energies of the d orbitals to change
Some of the d orbitals gain energy and some lose energy
In an octahedral complex, two (z2 and x2-y2) go higher and three go lower
In a tetrahedral complex, three (xy, xz and yz) go higher and two go lower
OCTAHEDRAL TETRAHEDRAL
3d 3d
The energy difference between the levels affects how much energy is absorbed when
an electron is promoted. The amount of energy governs the colour of light absorbed.
COLOURED IONS
The observed colour of a solution depends on the wavelengths absorbed
Copper sulphate solution appears blue because the energy absorbed corresponds to
red and yellow wavelengths. Wavelengths corresponding to blue light aren’t absorbed.
ENERGY CORRESPONDING TO
THESE COLOURS IS ABSORBED
RED
WHITE LIGHT
LIGHT
BLUE COLORIMETER
FILTER SOLUTION
FINDING COMPLEX ION FORMULAE USING COLORIMETRY
• a change of ligand can change the colour of a complex
• this property can be used to find the formula of a complex ion
• ight of a certain wavelength is passed through a solution
• the greater the colour intensity, the greater the absorbance
• the concentration of each species in the complex is altered
• the mixture with the greatest absorbance identifies ratio of ligands and ions
Unidentate form one co-ordinate bond Cl¯, OH¯, CN¯, NH3, and H2O
EDTA
HAEM
Co-ordination of CO molecules
interferes with the process
COMPLEX IONS - LIGANDS
6 Octahedral [Cu(H2O)6]2+
SIX FOLD
4 Tetrahedral [CuCl4]2-
FOUR FOLD
2 Linear [Ag(NH3)2]+
ISOMERISATION IN COMPLEXES
Some octahedral complexes can exist in more than one form
[MA4B2]n+
TRANS CIS
[MA3B3]n+
ISOMERISATION IN COMPLEXES
OPTICAL ISOMERISM
OPTICAL
ISOMERISM
ISOMERISATION IN COMPLEXES
OPTICAL
ISOMERISM
GEOMETRICAL
ISOMERISM
CIS TRANS
CATALYTIC PROPERTIES
Transition metals and their compounds show great catalytic activity
It is due to partly filled d-orbitals which can be used to form bonds with adsorbed
reactants which helps reactions take place more easily
Examples of catalysts
IRON Manufacture of ammonia - Haber Process
TRANSITION METAL
CHEMISTRY
THE END