Transition metals

Why are zinc and scandium NOT transition

metals?
Define a transition metal: d-block element that can form an
ION with a PARTIALLY FILLED d-orbital.

Scandium ion has no electrons in the d-orbital while zinc ion

has only a fully filled d-orbital so they don’t fit the definition
and so are not transition metals
Electron configuration of transition metals

*Remember 4s fills up before 3d except for Cr and

Cu
Special case of chromium and copper:
Chromium and copper behave differently as shown they do
not fit the pattern.
5 1
 Cr is [Ar] 3d 4s
10 1
 Cu is [Ar] 3d 4s

An electron from the 4s orbital goes down to the 3d orbital.

The reason this happens is it makes them more stable
NOTE: [Ar] is short hand for argons electron configuration we do
this so it’s easier to write out the EC of the metals we only write out
the 3d-orbitaland onward therefore,
[Ar]= 1s22s22p63s23p6

when writing out the EC of d-

block elements ions make sure
to remember that 4s loses
electron before the 3d orbital
Properties of transition elements:
These properties can only occur in transition elements.
 Variable oxidation states
 Form coloured compounds
 Form complex ions
 Can be used as catalysts

Variable oxidation states: this mean they can form

ions with different charges they can do this because the 4s
and 3d orbitals are so close together in terms of energy that
they can lose some form the 3d orbital as well.

Coloured compounds: this is due to the different

ions of TM so each different ion has a different colour.

Catalysis:
TM are good catalysts as they lose and receive
electrons in the d-orbital which speeds up a reaction.

There are two types of catalysts:

 Heterogeneous catalysts – a catalyst in the
different phase as the reactants.

General theory of how heterogeneous catalysts work is

that
 1. they can use their d-orbitals to carry out
adsorption (where the solid catalyst holds the
reactants molecules)
2. in this process, it weakens the bonds hence
lowering the activation energy for the reactants so
they can react quicker.
3. then desorption occurs (products leave the
surface of the catalyst).
Example:
Either Platinum, Palladium and rhodium are
the catalysts used in the catalytic converters
in cars.
1. The solid catalyst provides a surface for the NO,
CO molecules to come and
react.
2. It provides a surface for
adsorption to occur weakening
the bonds in the reactants and
causing them to react, lowering the activation
energy.
3. After adsorption, this leads to desorption (where
the products leave the surface of the catalysts).

Homogenous catalysts: when the catalyst

is in same phase as the reactants.
In homogeneous catalysis, the catalyst is
used up in the beginning steps of the
reaction then regenerated in another step
as a product.

this is the iodine clock experiment to make

this experiment go faster add Fe2+ as a
catalyst

complex ions and ligands

define
complex ion: central transition metal ion
surrounded by ligands
ligand: a molecule/ion that can form coordinate
bonds with the central transition metal ion.
Coordination number: the number of coordinate
bonds attached to the central transition ion.
Representing complex ions

This is the actual way

of showing a cr3+ ion is
when dissolved in
water. The
coordination number
for this ion would be 6
Monodentate ligands:

Mono dentate ligands can only form one coordinate

bond with the central TM.

Bidentate ligands:
Bidentate ligands are molecules that can form
two coordinate bonds with the central TM.

There are only two you need to know and you

have to know how to draw them
when drawing these molecules remember to
place the lone pair on the N and start the bond
from there

make sure you start the bond

from one lone pair on the
oxygen atom.

the coordination number of both of these

examples are still 6 as there are 6
coordinate bonds.

 NH2CH2CH2HN2 (ethyl-1,2-diamine, can be

shortened to en if you are told in question
that you can)

Shape of complex ions

Six coordinate bond complex ions

Octahedral
When a complex ion has six coordinate
bonds then it will all ways be in the shape of
an octahedral. With a bond angle 90o.

Four coordinate bond complex ions:

Tetrahedral
most of the time 4 dative bonds will have
a shape of, and have a bond angle of
109.50.
The main reason for TM metals to only
have 4 dative bonds are that chlorine
atoms are so large that only 4 fits around
the central TM.

Square planar
Sometimes 4 dative bonds can give a
square planar shape CN- ion are the
ligands are the most common to adopt
this shape. Bond angle is 90o.

How to tell whether to draw a compound as tetrahedral or square

planar
Usually the exam questions will always tell you for two ways they tell
you is
  Bond angle of [complex ion] is 90o draw the complex where it
shows tans isomerism.
 [complex ion] forms a square planar draw this ion.

Stereoisomerism in transition elements

Stereoisomerism in complex ion does not involve double bonds

instead it’s about the orientations of ligands around the central TM
ion. We only use CIS/TRANS when referring to complex ions.
CIS(z)= same
TRANS(E)= opposite
You will only ever get stereoisomerism questions with octahedral or
square planar.
Two methods of identifying cis or trans
Method 1:
1. identify the central TM atom and the two types of
ligands
2. then choose one ligand and see if the ligand opposite it
is the same if it is the same then then its trans if it’s
different then its cis
method 2:
1. identify the central transition metal ion and look at the
two different ligands surrounding it.
2. Determine the bond angle between two of the same
ligands if its 90o then its cis if its 180o then its trans
NOTE: this has to match for every ligand surrounding the
central atom

Square planar stereoisomerism:

 1. identify the central atom and the two types of
ligands.in this case its Cl and NH3
2. Then look at opposite ligands if the same ligands are
opposing each other than its trans(E) if they are not
then its cis(Z).
3. or Choose a ligand and identify the bond angle, in this
case the if Cl and Cl
are 90o apart then
cis but if Cl and Cl
are 180o apart then
its trans.

Cis-trans isomerism in octahedral complexes

Only monodentate ligands:
In this example, the octahedral complex only has
monodentate ligands surrounding the central atom with
these examples you will always have two of the same ligand
and 4 of the other ligand otherwise it can’t be a cis-trans
isomer.
1. identify the central
atom and the two
different ligands
2. then work out the
bond angle between
two of the same
ligands if 90 then cis if its 180 then is (trans).

Mondentate and bidentate ligands:

 In this example, this octahedral complex has both
monodentate and bidentate ligands surrounding the central
atom

1. find the central TM

atom then identify
the ligands present
2. look at the opposite
ligand and if they
are the same then
its trans but if they are different ligands then its cis. They
have to be the opposite and same for all ligands around
the atom for it to be trans.
3. Or you could look at the ligand and see the bonds
between two of the same ligands if 90o then its cis but
its. Its 180o then its trans.
Cis-platin
Cisplatin is and anti-cancer drug and works by killing fast
dividing cells this is the drug they use in
chemotherapy
1.Cis platin passes through the
membrane and the chloride ligands are
substituted by the water ligands
2.Then the cis platin binds to the DNA base
guanine by substituting the water ligand for a
nitrogen ligand on the guanine
 3.This changes the shape of DNA and stops it
from replicating

Side effects

 it can bind to healthy cells therefore damaging

them.
 Leads to hair loss as it damages hair follicle cells

Optical isomerism
Optical isomers sometimes called enantiomers are non-
superimposable mirror images of each other. Like you left
and right hand they are very similar but not the same.
Optical isomerism only occurs in octahedral
complexes containing two or more bidentate
ligands (you are asked in the exam to draw to
optical isomers of a compound).
Optical isomers can only occur with CIS
isomers

When asked to draw

optical isomers try view
the image as if it was
flipped symmetrically.

Ligand substitution reactions

Ligand substitution occurs when a ligand is displaced
by another that can make the complex more stable.
This can cause the structure of a compound to change
if the ligand that is substituted is of a different size.

There are different ligand substitution reactions:

Partial ligand substitution- this is where not all of

the ligands are substituted only a few are.

This reaction happens in steps first a few drops of

ammonia is added then a pale blue precipitate forms.
Then excess ammonia is added the precipitate
dissolves and a clear dark blue solution forms.

*this a reaction the exam wants

you to know specifically

Shape change- this is where the

complex ion changes shape due
to the ligand being a different size.in this case chlorine ions
are so big compared to water you can only fit 4 hence
changing the shape.

Full ligand substitution- this is where

all the ligands are swapped out with
different ligands.
The reaction below happens in steps
when a few drops of ammonia is
added then the violet solution turns
into a grey-green precipitate.
Then with excess ammonia the solution turns
clear purple. *this a reaction the exam wants you to
know specifically

Haemoglobin
Haemoglobin is used to transport oxygen around the body. Its initial
structure is that it has a central Fe(ii) ion surround by two different
ligands and has six coordinate bonds. when you breath in oxygen is
substituted in and then transported to the cells where it is
substituted by water ligand hence why we breath out water. But this
process can be disrupted by carbon monoxide. CO for a stronger
ligand bond so it can’t easily be substituted by oxygen so if oxygen is
transported to cells the person will die to oxygen deficiency.

Redox reactions
Qualitative analysis
Colours of all transition metals:
 Reactions with cations

Metal Dissolved in OH- OR Excess OH- Excess

s water NH3 NH3
Cu2+ [Cu(H2O)6]2+ Cu(OH)(H2O)4 Insoluble Dark
BLUE Pale blue blue
precipitate solution
Fe2+ [Fe(H2O)6]2+ Fe(OH)(H2O)4 Insoluble Insolubl
pale green Dirty green e
precipitate
Fe3+ [Fe(H2O)6]3+ Fe(OH)(H2O)4 Insoluble Insolubl
yellow Orange e
precipitate
Mn2+ [Mn(H2O)6]2+ Mn(OH)(H2O)4 Insoluble Insolubl
pale pink Pink e
precipitate
Cr3+ [Cr(H2O)6]3+ Cr(OH)(H2O)4 Cr(OH)63- Purple
violet Green-grey Dark solution
precipitate green
precipitat
e
Grey-green precipitate
 Reactions with halide ions sulphate ions and
carbonate and ammonium
Anion Test Result

Chlorine Add acidified White precipitate

silver nitrate
AgNO3
Bromine Add acidified Cream precipitate
silver nitrate
AgNO3
Iodine Add acidified Yellow precipitate
silver nitrite
AgNO3
Carbonate Add an acid and The limewater
bubble the gas goes cloudy
through
limewater
Sulphate Add acidified White precipitate
barium chloride should form
Ammonium Add NaOH Red litmus paper
bleaches red