Definition Melting points Density

An element that has its 'd' orbitals partly 1. Much denser than 's' block
filled, in some of its compounds. 1. All transition metals have elements.
Strictly speaking this means for example melting points above 2. Sc - Cu gradual increase in
in the first row of transition elements we 1000oC. This suggests density, this is due to an
include titanium to copper. 'd' block metallic bonding. increase in nuclear charge.
elements in say the first row (period 4) 2. 3d as well as 4s electrons 3. Metallic radius generally
include scandium to zinc. In some books available for delocalisation is decreases across a period
the phrases 'transition metal' and 'd' the best explanation for this, due to the increasing
block are synonymous. nuclear charge. At the same
since the more electrons
The transition metals resemble each time the Relative Atomic
other closely in their physical properties. within the 'sea' of electrons Mass (RAM) is increasing.
They are all hard, lustrous, weakly the greater the electrostatic
electropositive metals with high melting attraction, this, of course,
and boiling points. determines the melting
point of the metal. (see
Electronic configuration
Learn-It).

Electronic Configuration

Filling of 3d and 4s orbitals

Transition
In 'd' block, electrons are added to an
inner 'd' orbital and this shields the
outer 's' electrons from the increased
Metals
nuclear charge. Therefore, the atomic
radius decreases only slightly and
electronegativity and ionisation energies First Ionisation Energy
This property can be illustrated by the
increase only slightly.
examples below:
Fe2+ (3d6) is readily oxidised to Fe3+ (3d5) Energy required to form 1
The difference in energy between the
second and third shells is less than mole of gaseous ions, from 1
Mn2+ (3d5) is not readily oxidised to Mn3+
between the first and second. By the mole of gaseous atoms, with a
(3d4)
time the fourth shell is reached, there is, single positive charge.
in fact an overlap between the third and When transition metals form ions,
fourth shells. In other words, from electrons are lost first from the 4s sub- The first ionisation energies,
scandium onwards, the orbitals of shell rather than the 3d sub-shell. Thus across the first row of
highest energy in the third shell (the 3d Fe2+ ions have the electronic structure transition metals, are very
orbital) have higher energy than those of [Ar]3d6 rather than [Ar]4s23d4.
the lowest energy in the fourth shell (the similar due to them all losing
4s orbital). Hence, when writing the electrons from the 4s orbital
This occurs due to the presence of
electronic configurations of these 'd' electrons in the 3d level, these repel the rather than there partially
block elements we fill the 4s then the 3d 4s electrons even further from the filled 3d orbital’s (with the
orbitals. nucleus. Therefore, the 4s electrons are exception of Zn).
pushed to a higher energy level, higher
Exceptions do occur: than 3d. Consequently, when transition
atoms become ions, the electrons from
Cr [Ar] 4s13d5 the 4s level before the 3d.

Cu [Ar] 4s13d10 This means that all transition metals will

have similar chemical properties which are
This can be explained by the extra dictated by the behaviour of the 4s outer
stability offered by full and half-filled 'd'
electrons.
orbitals.
Transition Metals by James Davies and Rohan Kemp
Variable Oxidation States Stability of oxidation states Coloured Compounds
Properties 1. Stability of higher oxidation Formation
states decreases from left to
All transition metals except Sc are right. A possible reason is 1. Substances that are coloured will absorb
capable of bivalency. The 4s the increase in nuclear part of the electromagnetic spectrum and
electrons are first used and then 3d charge. reflect another.
electrons. 2. Relative stability of +2 and
+3 state Non-transition metal solutions tend to be
There is a great variety of oxidation colourless suggesting they absorb no part
states but patterns can be found. a) The increasing stability of +2 of the spectrum.
across the period is caused by the
Reason: Close similarity in energy of greater difficulty of removing a third 2. Compounds that are coloured have
4s and 3d electrons. Calcium, for electron as nuclear charge increases. electrons promoted from a ground state to
example, only has oxidation state an excited state. This energy transition
number +2 in compounds due to b) Mn2+/Mn3+ and Fe2+/Fe3+ have must coincide with the frequency of light
ease at which electrons are lost from stabilities that do not fit in this absorbed.
4s, but any further loss would need pattern. This can be explained by the
much greater energy since the third stability of 3d5 found in Fe3+ and For Na+ to excite electrons they must be
electron is to be found in an inner Mn2+.a promoted from their outer 2p orbital to a
shell. 3s orbital. This energy gap is too big.

Known oxidation states can be 3. In the case of Ti(H2O)63+ ions there is a

summarised by the table below. narrow gap in electron energy levels which
matches the energy inpart of the visible
Note: Mn can have an oxidation
state of +7 due to the hypothetical spectrum.
loss of 7 electrons (4s2 3d5) - after
this nuclear charge binds electrons
more strongly. Mn has the
maximum number of unpaired
electrons available for bond
formation. The number of unpaired
electron decreases steadily on either
side of Mn. Hence, the pattern
Naming complex ions
shown in the blue graph. This electron is not promoted to 4s since
the gap is too large. Instead the presence
1. Number ligands using mono,
All show oxidation state +2 (except of the water ligands causes the energy
di, tri, tetra, penta, hexa.
Sc) due to loss of two 4s electrons. symmetry of the 5 '3d' orbitals to distort
2. Identify ligands using names
and split into two levels.
ending in -o for anions. For
All show +3, but rare in Ni and Cu.
example: F- fluoro, CN-
The new energy gap matches part of the
cyano, Cl- chloro, OH-
Since, Transition metal ions are visible frequency (green/yellow) therefore
hydroxo (H2O is aqua, NH3 is
small they have a high charge the resulting solution appears purple.
ammine).
density, therefore, display similar
3. Name the cation using
properties to Aluminium. The principle is the same in other systems
English name in +ve complex
but details more complicated since there
but latinized name in -ve
are more electrons involved.
complex with suffix -ate. For
example: aluminate,
Different ligands affect the energetic
plumbate, cuprate, ferrate,
symmetry of 'd' orbitals differently
zincate, nickelate.
therefore, producing different colours.
4. Indicate oxidation number
of central cation using I, II, III
etc. Different oxidation states will vary colour
greatly due to different numbers of 'd'
electrons available.

Transition Metals by James Davies and Rohan Kemp

Paramagnetism Complex Ions Common complex ion reactions

Most substances are weakly repelled by a Tendency to form complex ions These reactions typically involve
strong magnetic field while others are weakly the replacement of a ligand by
attracted to it. When they are repelled, it is Complexes are atoms or more ions another ligand.
known as diamagnetism and when attracted or compounds in which an ion is
it is known as paramagnetism. surrounded by a number of Ligand replacement reactions.
molecules or oppositely charged
Paramagnetism arises because electrons can ions called ligands. A solution of copper (II) sulphate
be regarded as spinning on their axes and, is blue. This solution contains
just as an electric current flowing through a The ligands are joined to the central hydrated Cu2+ ions. The addition
wire generates a magnetic moment, so does atom or ion by co-ordinate bonds. of ammonia changes the solution
the spinning electron. The pair of electrons been donated to a dark blue containing the ion
by the ligand. The donor atoms are tetraammine copper (II).
Electrons that occupy the same orbital (i.e. usually oxygen, nitrogen and
have opposite spins), have, of course, zero halogens. The reaction can be summarised
magnetic moment since the two as shown below:
contributions cancel each other. The transition elements with vacant
'd' orbitals readily form complexes [Cu(H20)6]2+(aq) + 4NH3(aq) →
Heterogenous catalysis but, is not limited to these elements. [Cu(NH3)4(H20)2]2+(aq) + 4H20(l)

A catalyst enables a reaction to take a When potassium thiocyanate is

The most common ligands in added to a pale yellow solution of
different reaction pathway or mechanism of
complexes are: iron (III) ions, a deep blood red
a lower overall activation energy.
solution is formed, containing the
1. Water: most ions form hydrated ion pentaaquathiocyanato iron
Catalysts are regenerated at the end of a
ions in solution. (III).
reaction therefore a small amount of catalyst
will catalyse an infinite amount of reactants.
For example: [Cu(H20)6]2+ hexaaqua [Fe(H20)6]3+(aq) + SCN-(aq) →
Catalysts do take part in a reaction but are copper (II) ion [Cu(SCN)(H2O)5]2+(aq) + H2O(l)
not 'consumed'.
There are many more examples
Transition metals are considered to be good of ligand replacement (or
catalysts, due to their ability to form a exchange) reactions. You should
variety of different oxidation states and 'd' check with each syllabus for the
electrons allow adsorption onto their ones needed.
surface. This weakens bonds in reactant
molecules.
2. Ammonia: the co-ordinate bond Catalysis
Transition metals tend to be heterogeneous
is formed between the nitrogen
catalysts meaning, they are in a different
atom and the metal ion, the Students need to know about:
state (usually solid) than the products.
nitrogen atom donating the lone
pair of electrons. 1. How a catalyst works.
For example: Nickel powder is used in the
2. Homogeneous Catalysis
hydrogenation of C=C, as in ethene. Ni atoms For example: [Co(NH3)6]3+ 3. Heterogeneous Catalysis
provide sites for holding C=C and H2 in hexaammine colbalt (III) ion. 1. Physical
correct orientation for bonding.
adsorption and
chemisorption
2. Examples
3. Surface area
4. Catalyst Poisoning

Transition Metals by James Davies and Rohan Kemp

Half-equations and E

Half-equations allow us to predict whether a redox reaction will occur spontaneously or not. All half-
equations are measured against the standard electrode potential of Hydrogen.

Half-Equations

The best way to understand half-equations is to practice writing them out and balancing them. A half
equation shows how an ion is neutralised to an atom by the addition of electrons, water or hydrogen ions
only. Make sure that the molecules are all balanced; you need to check that your charges on either side
balance as well.

((Includes images and go over this bit again for me? For some dodgy reason, I couldn’t see the images you
sent in your word file. ))

Edexcel The OCR

This exam board like to include the chemistry of Sc and Exa

Zn in their transition metal unit. This is more of a m This exam board has some
comparison as to why they are not classified as transition differences in their syllabus when it
metals by looking at the compounds produced and how Boa
comes to ligand substitution. They
their chemistry differs to that of the other elements on rds. like you to work out expression of the
this row. stability constant Kstab with respect to
general ligand substitution:
They also include disproportionation in their syllabus as a
means of classifying reactions by oxidation number.: M2+(aq) + 6X-(aq) MX64-(aq)

The superoxide (O2-) ion is simultaneously oxidised and

reduced, by superoxide dismutase, to produce dioxygen
and hydrogen peroxide. Kstab = [MX64-(aq)]/[M2+(aq)][X-(aq)]6
The +1.5 oxidation state of the superoxide is oxidised to
A large Kstab relates to formation of a
dioxygen (O2) and reduced to form hydrogen peroxide
stable complex ion.
(H2O2).
AQA

AQA defines a transition metal as a d-block element which has at least one s-electron and at least one d-
electron but no p-electrons in its outer shell. As such, it includes Sc and Zn as transition metals.

For AQA, students also need to be able to rattle off the shapes of the transition metal ions (6, 4, and 2
coordinate).

AQA also look at specific examples of transition metals, such as haemoglobin, cisplatin and testing for
aldehydes and halide ions with Tollen’s reagent (Diammine silver (I) has the formula [Ag(NH 3)2]+ and is the
active ion in Tollen’s reagent.). Photography and electroplating are also looked at.

This exam board also explores TM compounds as catalysts in greater detail.

Transition Metals by James Davies and Rohan Kemp