Ib PPT 3 HL PDF

13.
1 First-row d-block elements
Higher level
OBJECTIVES
• Transition elements have variable oxidation states, form complex

ions with ligands, have coloured compounds, and display catalytic and
magnetic properties.
• Zn is not considered to be a transition element as it does not form
ions with incomplete d-orbitals.
• Transition elements show an oxidation state of +2 when the s-
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electrons are removed.
• Explanation of the ability of transition metals to form variable
oxidation states from successive ionization energies.
• Explanation of the nature of the coordinate bond within a complex
ion.
• Deduction of the total charge given the formula of the ion and
ligands present.
• Explanation of the magnetic properties in transition metals in terms
of unpaired electrons.
Transition metals
Higher level
• A transition element is defined as an element that
possesses an incomplete d-sublevel in one or more
oxidation states (ie. as an ion)
• All the elements in group 12, Zn, Cd, Hg, and Cn are
not transition metals as they contain full d-sublevels
with 10 d-electrons as ions (lose s electrons).
Transition metals
Higher level
• Transition metals have an empty d orbital. The d orbital
splits into two energy sublevels and electrons moving
between these gives them their properties
• Note: for Cr and Cu it is more energetically favourable
to half-fill and completely fill the d sub-level respectively
so they contain only one 4s electron
Properties
Higher level
• Produces colours and allows for complex ion formation
• It gives them variable oxidation numbers and makes
them good catalysts
• Most materials are diamagnetic (repelled by a
magnet), some transition metals are paramagnetic
(ferromagnetic – attracted by a magnet) due to unpaired
electrons allowing spin in one direction to form poles.
• When transition metals lose electrons they lose the

4s electrons first
• All transition metals can show an oxidation state of +2
and occurs when they lose both s orbital electrons
Oxidation numbers
Higher level
Variable oxidation states come from the fact that they
have relatively small differences in their successive
ionization energies. Cf. 1st and 2nd IE of Na vs one of
the transition metals.
Common oxidation states from the data booklet:
Electron configurations
Higher level
Element Z 3d 4s
Sc 21 [Ar]  
Ti 22 [Ar]   
V 23 [Ar]    
Cr 24 [Ar]      
Mn 25 [Ar]      
Fe 26 [Ar]      
Co 27 [Ar]      
Ni 28 [Ar]      
Cu 29 [Ar]      
Zn 30 [Ar]      
Higher level
Complex ions
A complex consists of a central atom, which
is usually a metal atom or ion, and attached
groups called ligands
The
coordination
number is the
total number of
points at which a
central atom or
ion attaches
ligands
Higher level
The region surrounding the central atom or
ion and containing the ligands is called the
coordination sphere
A substance
consisting of one
or more
complexes is
called a
coordination
compound
33
Higher level
• The number of lone pairs bonded to the metals
ion is known as the coordination number
Coordinati Shape
on
number
6 octahedral
4 tetrahedral
or square planar
2 linear
Square planar compounds are rare, but usually d8 configurations with strong field ligands.
Higher level
• Co-ordination number examples
Co- 6 4 2
ordination
number
Examples [Fe(CN)6]3- [CuCl4]2- [Ag(NH3)2]+

[Fe(OH)3(H2O)3] [Cu(NH3)4]2+
All of these complex ions are bonded to monodentate ligands

which means they all consist of one type of ligand.
4 lobes is normally tetrahedral, but with full d8 (Cu) and strong
ligands it is square planar.
Higher level
Ligands
• A ligand is a neutral molecule or anion which
contains a non-bonding pair of electrons, these
electron pairs, from the ligand, form coordinate
bonds with the metal ion to form complex ions
• Complex ions form with transition metals
because of their small size d-block ions attract
species that are rich in electrons
Higher level
Coordinate bonds and numbers
A common ligand is
water and most (but not
all) transition metal ions
exist as hexahydrated
complex ions in
aqueous solution, e.g.
[Fe(H2O)6]3+
(1) The lone pair of electrons from the water

molecules (ligands) form the coordinate bonds.
(2) Iron is forming 6 bonds, so the coordination
number of the iron is 6
Higher level
EDTA
• Ethylenediaminetetraacetate (EDTA) is a
chelate or polydentate ligand as it grabs onto
the metal with more than one donor atom.
• It has several important uses including the
removal of heavy metal ions such as
treatment for lead poisoning, as well food
preservation in preventing transition metals
catalyzing food rancidity (going off).
13.2 Coloured complexes
Higher level
OBJECTIVES
• The d sub-level splits into two sets of orbitals of different

energy in a complex ion.
• Complexes of d-block elements are coloured, as light is
absorbed when an electron is excited between the d-orbitals.
• The colour absorbed is complementary to the colour observed.
• Explanation of the effect of the identity of the metal ion, the
oxidation number of the metal and the identity of the ligand on
the colour of transition metal ion complexes.
• Explanation of the effect of different ligands on the splitting of
the d-orbitals in transition metal complexes and colour observed
using the spectrochemical series.
Crystal field theory (CFT)
Higher level
CFT suggest that the dxy, dyz, dxz orbitals are of a
lower energy state (more stable) than the
and orbitals creating a split d-sublevel.
The x, y, z axis is
where the atomic axis
where ligands join.
Ligands and energy levels
Higher level
Strong field ligands cause spin paired splitting
which has higher energy levels as the electrons in
the ligands are repelling the electrons in the
metal which are on the same axis.
These orbitals
wwww.mrwengibchemistry.com are not
directly in line
with the
ligands.
Crystal field splitting energy (∆0)
Higher level
The free electron pair orbitals of
the ligands are attracted to the
nucleus of the metal cation. The
overlapping orbitals with the
and can cause
electrons to move to the split
lower energy orbitals of dxy, dyz,
dxz which do not have direct
overlap with the ligands. This
difference in energy is the ∆0 and
varies in size, hence movement
of electrons between these split
d orbitals will produce different
wavelengths (seen as different
colours).
Higher level
1. ∆0 and ligand strength
More negative
charge density in
ammonia makes ∆0
greater than than
water.
Similarly, as fluorine
has more electron
density than
chlorine, so ∆0
increases.
Higher level
2. ∆0 and metal ions
Descending down a
group the ∆0
increases due to
more orbital
overlap.
Higher level
3. ∆0 and oxidation state
The higher the
oxidation state of
the cation the more
∆0 increases due to
greater attraction of
the nucleus to the
ligand and hence
more orbital
overlap.
Crystal field splitting energy (∆0)
Higher level
The crystal field splitting energy is the difference
in energy between these two split sublevels.
Ligands and ∆0
Higher level
The strength of the ligand determines the
amount of splitting. Splitting can be spin free or
spin paired.
HIGH energy split, low spin LOW energy split, high spin
Diamagnetism and paramagnetism
Higher level
Eg. CN is a strong-field ligand creating
diamagnetism, H2O is a weak field ligand creating
paramagnetism.
diamagnetic paramagnetic
Electron configurations and ∆0
Higher level
The lower energy state is written as and the
higher energy state is written as .
The configurations are written as follows:
Spectrochemical series
Higher level
The spectrochemical series (from data booklet)
shows the splitting strength of the ligands:
Weak field ligands Strong field ligands
M3+ M2+
metal metal
ion ion
Weak field ligands cause spin free splitting, <∆0.

Strong field ligands cause spin paired splitting, >∆0.
Incomplete square planar explanation
Higher level
d8 configurations with strong field
ligands (low spin) will look like this 
Hence with the greater repulsion on the lower energy orbitals, the
ligands will best line up on the x and y axis of the dx2-y2(square
planar) to be as far apart from each other as possible (rather than
dz2) or in a tetrahedral shape.
Other configurations
Higher level
4 lobes
2 lobes
6 lobes
Linear as z2 is slightly closer to nucleus

Square planar – d8 with strong ligand (Cu)
Tetrahedral as visually looks like the easiest acess to the nucleus with a 3D model
Octahedral – only symmetrical place for 6 ligands
Colours
Higher level
• Many complex ions are colored because the energy
differences between d orbitals match the energies of
components of visible light
• The colour absorbed can be determined by taking
the colour transmitted (observed) and finding the
opposite wavelength on the colour wheel (from data
booklet).
Yellow light transmitted
Violet light absorbed

Why?
Higher level
Corundum Al2O3 Ruby Al2O3: 1% Cr3+

Higher level
Why?
Higher level
Beryl Be3Al2Si6O18 Emerald Be3Al2Si6O18: 1% Cr3+

Higher level
Different colours of chromium – induce the
Higher level
strength of the ligand…

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13.

1 First-row d-block elements

• Transition elements have variable oxidation states, form complex

• When transition metals lose electrons they lose the

Examples [Fe(CN)6]3- [CuCl4]2- [Ag(NH3)2]+

All of these complex ions are bonded to monodentate ligands

(1) The lone pair of electrons from the water

• The d sub-level splits into two sets of orbitals of different

Weak field ligands cause spin free splitting, <∆0.

Linear as z2 is slightly closer to nucleus

Violet light absorbed

Corundum Al2O3 Ruby Al2O3: 1% Cr3+

Beryl Be3Al2Si6O18 Emerald Be3Al2Si6O18: 1% Cr3+

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