5.3.

1 Transition Elements
Sc 1s22s22p63s23p6 4s23d1 Sc 3+ [Ar] 4s03d0
General properties of transition metals Ti 1s22s22p63s23p6 4s23d2 Ti 3+ [Ar] 4s03d1
V 1s22s22p63s23p6 4s23d3 V 3+ [Ar] 4s03d2
transition metal characteristics of elements Ti 
Cu arise from an incomplete d sub-level in ions Cr 1s22s22p63s23p6 4s13d5 Cr 3+ [Ar] 4s03d3
Mn 1s22s22p63s23p6 4s23d5 Mn 2+ [Ar] 4s03d5
Fe 1s22s22p63s23p6 4s23d6 When Fe 3+ [Ar] 4s03d5
these characteristics include Co 1s22s22p63s23p6 4s23d7 forming Co 2+ [Ar] 4s03d7
•formation of coloured ions, ions lose
Ni 1s22s22p63s23p6 4s23d8 4s before Ni 2+ [Ar] 4s03d8
•variable oxidation state
Cu 1s22s22p63s23p6 4s13d10 3d Cu 2+ [Ar] 4s03d9
•catalytic activity.
Zn 1s22s22p63s23p6 4s23d10 Zn 2+ [Ar] 4s03d10
•Complex ion formation,

Why is Zn not a transition metal?

Zn can only form a +2 ion. In this ion the Zn 2+ has a complete d orbital and so
does not meet the criteria of having an incomplete d orbital in one of its ions.

Why is Sc not a transition metal?

Sc can only form a +3 ion. In this ion the Sc3+ has an empty d orbital and so does not
meet the criteria of having an incomplete d orbital in one of its ions.

Typical Properties of Transition metals

The existence of more than one oxidation state for each element in its compounds
For example iron commonly forms +2 and +3, chromium commonly forms +2,+3 and +6
see page 5 of this guide for more detail.

The formation of coloured ions

There are characteristic colours for each transition metal element and the colours can
vary in the different oxidation state. See the rest of the guide for many examples.

The catalytic behaviour of the elements and their compounds and their
importance in the manufacture of chemicals by industry
Iron is used as a catalyst in the Haber process to produce ammonia. Manganese dioxide
MnO2 catalyses the decomposition of hydrogen peroxide. Vanadium pentoxide V2O5
catalyses the contact process . See 3.2.2 reaction rates for some more detail.

Complex formation
2+
complex :is a central metal ion surrounded by ligands. OH2
H2O OH2
ligand.: An atom, ion or molecule which can donate a lone electron pair
Cu
H2O OH2
Co-ordinate bonding is involved in complex formation.
Co-ordinate bonding is when the shared pair of electrons in the covalent bond OH2
come from only one of the bonding atoms.
Co-ordination number: The number of co-ordinate bonds formed to a central
metal ion.

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ligands can be unidentate (e.g. H2O, NH3 and Cl- ) 3+
A complex with bidentate
CH2
which can form one coordinate bond per ligand or NH2
ligands e.g.
H2 C [Cr(NH2CH2CH2NH2)3]3+
bidentate (e.g. NH2CH2CH2NH2 and ethanedioate NH2 NH2 CH2
ion C2O4 2- ) which have two atoms with lone pairs Cr
CH2 There are 3 bidentate
and can form two coordinate bonds per ligand NH2 NH2
ligands in this complex
or multidentate (e.g. EDTA4- which can form six NH2
H2 C each bonding in twice
coordinate bonds per ligand). CH2 to the metal ion
The EDTA4- anion has the formula
It has a coordination number of 6
O O
-O C CH2 CH2 C O- O

C 3-
N CH2 CH2 N O
C O
A complex with
-O C CH2 CH2 C O- O O O
C bidentate ethanedioate
Cr
C ligands e.g. [Cr(C2O4)3]3-
O O O O O

with six donor sites(4O and 2N) and forms a 1:1 O C O

complex with metal(II) ions C

O

Learn the two bidentate ligands

Equations to show formation of bidentate and mutidentate complexes mentioned above but it is not
Cu(H2O)62+ + 3NH2CH2CH2NH2  [Cu(NH2CH2CH2NH2)3]2+ + 6H2O necessary to remember the
structure of EDTA
Cu(H2O)62+ + 3C2O42- [Cu(C2O4)3]4- + 6H2O
Cu(H2O)62+ + EDTA4- [Cu(EDTA)]2- + 6H2O

Shapes of complex ions

transition metal ions
transition metal ions commonly form square planar Ag+ commonly forms
commonly form octahedral tetrahedral complexes complexes are also linear complexes
complexes with small with larger ligands formed, e.g. e.g. [Ag(NH3)2]+,
ligands (e.g. H2O and NH3). (e.g.Cl- ). cisplatin [Ag(S2O3)2]3- and
[Ag(CN)2]- (all
[Co(NH3)6]2 [Cu(H2O)6]2+ [CoCl4]2-
colourless).
2+ Cl 2-
NH3 H 3N Cl
H3 N NH3 Pt +
Ni Cu H 3N H3 N Ag NH3
H3 N Cl
NH3
NH3 Cl Cl
Cl
Isomerism in complex ions

Complexes can show two types of stereoisomerism: cis-trans isomerism and optical isomerism

Cis-trans isomerism in square planar complexes

H3N NH 3 H3N Cl
Ni Ni
Cl Cl Cl NH 3
Cis-Ni(NH3)2Cl2 trans-Ni(NH3)2Cl2

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 Cis-trans isomerism in octahedral complexes

OH2 OH2
+ +
H2O ClH
HCl ClH 2+
2+
Cr Cr
H2O
OH2
HCl OH2
OH2 OH2

trans-[Cr(H2O )4Cl2]+
Cis-[Cr(H2O )4Cl2]+

Optical isomerism Complexes with 3 bidentate ligands can form two optical
isomers (non-superimposable mirror images).
2+
2+
CH2 CH2
NH2 H2N CH2
H2C
NH2 NH2 CH2 NH2
H2C -
NH2
Ni Ni
CH2
NH2 NH2 H2C NH2 NH2
NH2
H2C NH2 CH
CH2 2
CH2

Platin binds to DNA of cancer cells and

Cisplatin
stops cancer cells dividing.
The Pt(II) complex cisplatin is used as an anticancer drug.
H 3N Cl Cl NH3
The cisplatin version only works as two chloride ions are displaced and the
molecule joins on to the DNA. In doing this it stops the replication of Pt Pt
cancerous cells. H 3N Cl H 3N Cl
In the body one Cl ligand is subsituted by a water molecule
Pt(NH3)2Cl2 + H2O  [Pt(NH3)2Cl(H2O)]+ + Cl– cisplatin transplatin
It can also prevent the replication of
Be able to apply your knowledge of bonding to given information in the
healthy cells by bonding on to
question to explain how it bonds to DNA molecule- generally a
healthy DNA which may lead to
combination of dative covalent bonding and hydrogen bonding.
unwanted side effects like hair loss.

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Ligand substitution

Reaction with excess NH3

With excess NH3 ligand substitution reactions occur with several transition aqueous ions.

[Cu(H2O)6]2+(aq) + 4NH3 (aq)  [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O (l) Note: This substitution in the case with
deep blue solution Cu is incomplete as not all the water
blue solution molecules are substituted.

Be able to write equations for other metal ions given

The ligands NH3 and H2O are similar in size
information about the complex formed. No need to learn
and are uncharged. Ligand exchange
colours for these other ions.
occurs without change of co-ordination
[Co(H2O)6]2+(aq) + 6NH3 (aq)  [Co(NH3)6]2+ (aq) + 6H2O (l) number for Co and Cr

Reactions with Chloride ions

Addition of a high concentration of chloride ions (from conc HCl or Addition of conc HCl to aqueous ions of
saturated NaCl) to an aqueous ion leads to a ligand substitution Cu and Co lead to a change in
reaction. coordination number from 6 to 4.
The Cl- ligand is larger than the uncharged H2O and NH3
ligands so therefore ligand exchange can involve a [Cu(H2O)6]2+ + 4Cl-  [CuCl4]2- + 6H2O
change of co-ordination number. blue solution yellow/green solution
Be careful: If solid copper chloride (or any other metal )is
[Co(H2O)6]2+ + 4Cl-  [CoCl4]2- + 6H2O
dissolved in water it forms the aqueous [Cu(H2O)6]2+ complex
and not the chloride [CuCl4]2- complex pink solution blue solution

Biological Complexes

Fe(II) in haemoglobin enables oxygen to be transported in the blood . Haem is an iron(II) complex with a
multidentate ligand. O2 bonds to Fe2+ ions in the Haemoglobin and when required the O2 is released.

CO is toxic to humans as CO can from a strong coordinate bond with haemoglobin. This is a stronger
bond than that made with oxygen and so it prevents the oxygen attaching to the haemoglobin. With CO,
the stability constant is greater than with complex in O2.

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 Precipitation Reactions with sodium hydroxide and ammonia
The bases OH- and ammonia when in limited These reactions are classed as
amounts form the same hydroxide precipitation reactions
precipitates.

[Cu(H2O)6]2+ (aq) + 2OH- (aq)  Cu(H2O)4(OH)2 (s) + 2H2O (l) Cu2+ (aq) + 2OH- (aq)  Cu(OH)2 (s)
Blue solution blue ppt Blue solution blue ppt
[Mn(H2O)6]2+ (aq) + 2OH- (aq)  Mn(H2O)4(OH)2 (s) + 2H2O (l) Mn2+ (aq) + 2OH- (aq)  Mn(OH)2 (s)
Very pale pink solution Pale brown ppt Very pale pink solution Pale brown ppt

[Fe(H2O)6]2+ (aq) + 2OH- (aq)  Fe(H2O)4(OH)2 (s) + 2H2O (l) Fe2+ (aq) + 2OH- (aq)  Fe(OH)2 (s)
green ppt green solution green ppt
green solution

[Fe(H2O)6]3+ (aq) + 3OH- (aq)  Fe(H2O)3(OH)3 (s) + 3H2O (l) Fe3+ (aq) + 3OH- (aq)  Fe(OH)3 (s)
brown ppt brown ppt
Yellow/brown solution Yellow/brown solution

[Cr(H2O)6]3+ (aq) + 3OH- (aq)  Cr(H2O)3(OH)3 (s) + 3H2O (l) Cr3+ (aq) + 3OH- (aq)  Cr(OH)3 (s)
green solution green ppt green solution green ppt

With ammonia when added in limited amounts the same hydroxide precipitates form. The ammonia
acts as a base, removes a proton from the aqueous complex and becomes the ammonium ion
[Mn(H2O)6]2+ (aq) + 2NH3 (aq)  Mn(H2O)4(OH)2 (s) + 2NH4+ (aq)

[Fe(H2O)6]3+ (aq) + 3NH3 (aq)  Fe(H2O)3(OH)3 (s) + 3NH4+ (aq)

Reaction with excess OH-

•This hydroxide is classed as amphoteric
With excess NaOH, the Cr hydroxide dissolves. because it can react with alkali to give a solution
Cr becomes [Cr(OH)6]3- (aq) green solution and react with acid to form the aqueous salt.

Cr(H2O)3(OH)3 (s) + 3OH- (aq ) [Cr(OH)6]3- (aq) + 3H2O(l) Cr(H2O)3(OH)3 (s) + 3H+ (aq ) [Cr(H2O)6]3+(aq)

Reaction with excess NH3

With excess NH3 ligand exchange reactions occur with Cu and Cr, and their hydroxide precipitates
dissolve in excess ammonia

The ligands NH3 and H2O are similar in size and are
uncharged. Ligand exchange occurs without change of Cr becomes [Cr(NH3)6]3+ purple solution
co-ordination number for Cr

This substitution may, however, be incomplete Cu becomes [Cu(NH3)4(H2O)2]2+ deep blue solution
as in the case with Cu

Cr(OH)3(H2O)3(s) + 6NH3 (aq)  [Cr(NH3)6]3+(aq) + 3H2O(l) + 3OH- (aq)

Cu(OH)2(H2O)4(s) + 4NH3 (aq)  [Cu(NH3)4(H2O)2]2+ (aq) + 2H2O (l) + 2OH- (aq)

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Variable Oxidation States
When transition metals form ions they
Transition elements show variable oxidation states lose the 4s electrons before the 3d

Iron (II) Oxidation

Fe2+ (green solution) can be easily oxidised to Fe3+ (brown solution) by various oxidising agents. We
commonly use potassium manganate (VII), although oxygen in the air will bring about the change

MnO4-(aq) + 8H+ (aq) + 5Fe2+ (aq)  Mn2+ (aq) + 4H2O (l) + 5Fe3+ (aq)
Purple colourless

Iron (III) Reduction

Fe3+ (brown solution) can be reduced to Fe2+ (green solution) by various reducing agents. We commonly
use potassium iodide solution. The brown colour of the iodine formed can mask the colour change of the Iron.
2Fe3+ (aq) + 2I- (aq)  I2(aq) + 2Fe2+ (aq)

Reducing Chromium
Cr3+ (green) and then Cr2+ (blue) are formed by reduction of Cr2O72- (orange) by the strong reducing agent
zinc in (HCl) acid solution. Fe2+ is a less strong reducing agent and will only reduce the dichromate to Cr3+

Cr2O72- + 14H+ + 6Fe2+  2Cr3+ + 7H2O + 6 Fe3+ The Fe2+ and Cr2O7 2- in acid solution reaction can be
Orange green used as a quantitative redox titration. This does not
need an indicator

Oxidising Chromium
When transition metals in low oxidation states are in alkaline It is easier to remove an electron
solution they are more easily oxidised than when in acidic solution from a negatively charged ion

Excess NaOH
[Cr(H2O)6]3+ (aq) [Cr(OH)6]3- (aq) Alkaline chromium(III) can be oxidised by
Acidified alkaline using oxidising agents such as hydrogen
Not easy to oxidise easier to oxidise peroxide to the (yellow solution) chromate ion

H2O2 Reduction :H2O2 + 2e-  2OH-

Cr(OH)63- (aq) CrO42- (aq) Oxidation: [Cr(OH)6]3- + 2OH- CrO42- + 3e- + 4H2O
Green solution yellow 2 [Cr(OH)6]3- + 3H2O2 2CrO42- +2OH- + 8H2O
solution

Reduction of Cu2+ to Cu+

Cu2+ (blue solution) can be reduced to Cu+ by various reducing agents. We commonly use potassium
iodide solution. 2Cu2+ (aq) + 4I- (aq)  I2(aq) + 2CuI (s)
Brown White
solution precipitate

Disproportionation of copper(I) ions

Copper(I) ions when reacting with sulfuric acid will disproportionate to Cu2+ and Cu metal
2Cu+  Cu + Cu2+ Full Equation Cu2O + H2SO4  CuSO4 + Cu + H2O
Cu+(aq) + e−  Cu(s) Eo
= +0.52 V As Eo Cu+/Cu > Eo Cu2+/Cu+ and Ecell has a positive
Cu2+(aq) + e−  Cu+(aq) Eo = +0.15 V value of +0.37V , Cu+ disproportionates from +1
So Eo cell = 0.52 − 0.15 = +0.37 V oxidation state to 0 in Cu and +2 in Cu2+

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