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Transition Elements

Introduction
Definition
-

Transition element: d-block element that forms at least 1 ion with a partiallyfilled d-subshell
i.e. Scandium (Sc3+: [Ar] 3d04s0) and Zinc (Zn2+: [Ar] 3d10 4s0) are technically not
counted as transition metals

Sc: [Ar] 3d14s2 Sc3+: [Ar] 3d04s0

Zn: [Ar] 3d104s0 Zn2+: [Ar] 3d104s0

Scandium only forms Sc3+ which has a 3d0 configuration in all its compounds
Zinc only forms Sc2+ which has a 3d10 configuration in all its compounds

Electronic Configuration of Transition Elements


First row transition elements have similar electronic configuration of [Ar] 3d x4sy
where [Ar] =1s22s22p63s23p6 and 1x10 and y=2. Chromium and copper is an
exception where y=1
In period 4, an empty 4s orbital has a lower energy than an empty 3d orbital.
Thus the 4s orbital is filled first before the 3d orbital, according to Aufbau
principle

Element No. of e-

Electronic
Configuration

Ca

20

[Ar]4s2

Sc

21

[Ar]3d14s2

Ti

22

[Ar] 3d24s2

23

[Ar] 3d34s2

Cr

24

[Ar] 3d54s1

Mn

25

[Ar] 3d54s2

Fe

26

[Ar] 3d64s2

Co

27

[Ar] 3d74s2

Ni

28

[Ar] 3d84s2

Cu

29

[Ar] 3d104s1

Zn

30

[Ar] 3d104s2

Maximum Oxidation
State

Representation
[Ar]

[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]

+2
+3
+4
+5
+6
+7
+6
+5
+4
+3
+2

Maximum oxidation state given by the number of unpaired 3d electrons + 4s


electrons

Anomalous Electronic Configurations


-

Cr and 29Cu have only 1 4s electrons because it a half-filled 3d 5 or completely


filled 3d10 orbitals are favourable arrangements of electrons respectively
24

3d

4s

Cr: 3d and 4s orbitals are very close in energies. Occupancy of orbitals is


determined by inter-electron repulsions rather than energy differences between
orbitals

Formation of Cations
-

Empty 3d orbitals are of higher energy level than empty 4s orbitals 4s


orbitals are filled up first
Filled 3d orbitals are of lower energy level than filled 4s orbitals 4s
orbitals are lost first
Filled 4s orbitals behave as outermost, highest-energy orbital and 4s electrons
become the valence electrons in cations, valence 4s electrons are lost first,
followed by 3d electrons
Fe:
Fe2+:
Fe3+:

- Physical Properties
-

Effective nuclear charge


-

is relatively invariant across transition elements

trend
explan
ation

Across period 4 main group


elements
Increases significantly
Nuclear charge increases
due to increasing number of
protons. Nuclear charge
increases
Electrons are added to
same outermost shell.
Nuclear charge increases
but shielding effect from
inner electrons remain
relatively constant
Increase in nuclear charge
outweighs negligible
increase in shielding effect
from inner electrons
Effective nuclear charge
increases significantly

Across first row transition


elements
Relatively Invariant
Nuclear charge increases
due to increasing number of
protons.
Electrons are added to
penultimate 3d orbitals.
Nuclear charge increases
Increase in shielding effect
from 3d electrons almost
cancels out increase in
nuclear charge
Effective nuclear charge
remains relatively invariant

Atomic radii

Trend: atomic radii are relatively invariant across transition elements

trend
explan
ation

Across first row transition


elements
Relatively Invariant
Nuclear charge increases
due to increasing number of
protons.
Electrons are added to
penultimate 3d orbitals.
Nuclear charge increases
Increase in shielding effect
from 3d electrons almost
cancels out increase in
nuclear charge
Effective nuclear charge
remains relatively invariant
Atomic radius remains
relatively invariant

S-block elements
-

Across period 4 main group


elements
Decreases significantly
Nuclear charge increases
due to increasing number of
protons. Nuclear charge
increases
Electrons are added to
same outermost shell.
Nuclear charge increases
but shielding effect from
inner electrons remain
relatively constant
Increase in nuclear charge
outweighs negligible
increase in shielding effect
from inner electrons
Effective nuclear charge
increases significantly
Atomic radius decreases
significantly

Transition metals has smaller atomic radii than s-block metals from
same period
Across Period 4, NC increases due to increase in number of protons.
Within transition metals, each additional electron enters penultimate
3d shell.
Although 3d electrons shield outer 4s electrons from nuclear charge, 3d
electrons provide a poor shield between outermost 4s electrons and the
nucleus
Valence electrons are still strongly attracted by the nucleus

Increase in effective nuclear charge across Period 4 results in smaller


atomic radii for transition metals

Ionic radii

Ionic radii are relatively invariant across transition elements

Ionic radius is not a fixed property of any given metal ion but varies with
many other parameters like magnitude of positive charge, coordination
number, spin state etc.

General trends

Ionic radius decrease as magnitude of positive charge increase


Ionic radius increases as magnitude of negative charge increase
Among cations with the same positive charge, ionic radii remain relatively
invariant across transition elements

S-block elements
-

TM has smaller atomic radii than s-block metals of same period

Increase in ENC across Period 4 draws electrons closer to the nucleus


Results in smaller ionic radii for transition metal ions as compared to sblock metal ions of the same charge

First ionisation energy


-

First ionisation energies remain relatively invariant across transition


elements

Across period 4 main group


elements
- Increases significantly
- 1st IE involves the removal of
outermost 4s or 4p electrons
- Nuclear charge increases
due to increasing number of
protons. Nuclear charge
increases
- Electrons are added to
same outermost shell.
- Nuclear charge increases
but shielding effect from
inner electrons remain
relatively constant
- Increase in nuclear charge
outweighs negligible
increase in shielding effect
from inner electrons
- Effective nuclear charge
increases significantly
- Energy needed to remove
outermost electron increases
significantly

Across first row transition


elements
- Relatively Invariant
-1st IE involves removal of
outermost 4s electrons
- Nuclear charge increases
due to increasing number of
protons.
- Electrons are added to
penultimate 3d orbitals.
- Nuclear charge increases
Increase in shielding effect
from 3d electrons almost
cancels out increase in
nuclear charge
- Effective nuclear charge
remains relatively invariant
- Energy needed to remove
outermost electron remains
relatively invariant

trend
expla
natio
n

Anomaly: zinc

Zn has a significantly higher first IE than other d-block elements.


-

Cu: [Ar] 3d10 4s1 1st IE = 745 kJ mol-1

Zn: [Ar] 3d10 4s2 1st IE = 906 kJ mol-1

- 1st IE involves removal of a 4s electron


- Zn has 1 more proton than Cu, hence has a stronger nuclear charge
- From Cu to Zn, the electron is added to the valence 4s orbital, which experiences
the same shielding from inner electrons. They have the same number of inner
shell electrons, hence same shielding effect
-

ENC then increases 4s electron is held more closely to the nucleus, hence
more energy is needed to remove a valence electron from Zn

S-block elements
-

Transition elements have higher first ionisation energies than s-block


metals of the same period

Across TE,

Across Period 4, NC increases due to increase in number of protons.


Within transition metals, each additional electron enters penultimate
3d shell.
Although 3d electrons shield outer 4s electrons from nuclear charge, 3d
electrons provide a poor shield between outermost 4s electrons and the
nucleus
Valence electrons are still strongly attracted by the nucleus

Increase in effective nuclear charge across Period 4. More energy is


needed to remove a valence electron from a transition metal atom than
from an s-block metal atom

1st and 2nd are relatively invariant

3rd and 4th generally increase

- 2nd, 3rd and 4th IE shows a peak at Cr+, Mn2+ and Fe3+ respectively
o All 3 ions share the same configuration of [Ar] 3d 5, where the d electrons
are unpaired and are in singly orbitals
-

Subsequent d-electrons have to share an orbital occupied by an electron


interelectronic repulsion exists in the d electron being removed from Mn +, Fe2+
and Co3+ (adjacent to Cr+, Mn2+ and Fe3+)

Density

Trend: across transition metals, density generally increases.

- Across transition elements, atomic mass increases


- Atomic radius remains relatively invariant density generally increases
-

Other factors include the crystal structures

S-block elements

Transition elements are much denser than s-block elements

Tre
nd
Rea
son

s-block elements
- Low
-

Smaller atomic mass


Large atomic radius
Fewer atoms per unit
volume

Transition elements
- Very high
-

Higher atomic mass


Small atomic radius
Closely packed metallic
structure results in more
atoms per unit volume

Melting and boiling points

Trend: transition elements have higher m.p. and b.p. than s-block elements

Tre
nd
Rea
son

s-block elements
- Generally Lower
-

only 1 or 2 valence electrons


from 4s orbitals are available
for delocalisation
less energy is required to
overcome weaker metallic
bonding i.e. electrostatic
forces of attraction between
the metal cations and sea of
delocalised 4s valence
electrons

Transition elements
- generally higher
-

both 3d and 4s valence


electrons are available for
delocalisation due to their
proximity in energies
more energy is required to
overcome stronger metallic
bonding i.e. electrostatic
forces of attraction between
the metal cation and sea of
delocalised 3d and 4s
valence electrons

Mechanical properties

Higher tensile strength can withstand stress while being stretched/pulled


before breaking

More malleable readily beaten into shape

More ductile can be drawn into a wire


-

Due to stronger metallic bonding


Layers of closely packed atoms slide over each other without disrupting
stronger electrostatic attraction between cations and delocalised electrons

Electrical and thermal conductivity

Lower conductivities than s-block elements in the same period, except Cu


-

Calcium

- Copper
- Very good conductor
- Good conductor
- Both 4s and inner 3d electrons are
- Inner shell electrons are not available
available for delocalisation due to
for delocalisation as they are very
their proximity in energies
different in energies from the valence
- Note: not all 3d electrons are
electrons
delocalised and used in conduction
- Fewer electrons are available to
- More electrons are available to
conduct current/heat
conduct a current/heat

- Chemical properties
-

Trends in Oxidation States


-

TM possess variable oxidation states while s-block elements are limited to


oxidation states of +1 (Group I) or +2 (group II)

Elem
ent
- Ca
- Sc
- Ti

Electronic
Configuration
- [Ar]4s2
- [Ar]3d14s2
- [Ar] 3d24s2

[Ar] 3d34s2

Cr

[Ar] 3d54s1

Mn

[Ar] 3d54s2

Oxidation State
- +2
- +3
+1, +2, +3, +4
+1, +2, +3, +4,
+5
+1, +2, +3, +4,
+5, +6
+1, +2, +3, +4,
+5, +6, +7

Fe

[Ar] 3d64s2

Co

[Ar] 3d74s2

Ni
Cu
Zn

[Ar] 3d84s2
[Ar] 3d104s1
[Ar] 3d104s2

+1, +2, +3, +4,


+5, +6
- +1, +2, +3, +4,
+5
- +1, +2, +3, +4
- +1, +2, +3
- +2

In transition elements:
4s and 3d electrons are of similar energy
when 4s electrons are removed, some or all of 3d electrons may also be
removed or shared without requiring much more energy
In s-block elements:
When the outermost electrons in s orbitals are removed, a stable noble gas
configuration is obtained
Subsequent removal of electrons would be from inner shell p orbitals which
requires too much energy
Further ionisation is then not favourable

Max O.S. = no. of 4s electrons + no. of unpaired 3d electrons


No. of available O.S. increases from Sc (+3 only) to Mn (+7, from +1 to +7)
and decreases to Zn ( +2 only)
- Mn has the most number of oxidation states
- After Mn (3d5) Pairing of 3d electrons occurs and no. of unpaired 3d electrons
available for covalent bond formation decreases
- All first row d-block elements show an oxidation state of +2 which
corresponds to the loss of two 4s electrons
except Sc, [Ar]3d14s2 since it is more favourable to lose all 3 electrons to
form a stable noble gas configuration of [Ar]
- All first row d-block elements show an oxidation state of +3 which
corresponds to the loss of one 3d and two 4s electrons
- except Zn, [Ar] 3d104s2 since it is more difficult to remove 3d electrons
from 3d orbitals as 3d orbitals become significantly lower in energy than
4s orbitals as nuclear charge increases
- At lower O.S., transition elements exist as cations in ionic compounds
- E.g. Cu2+ in CuSO4, Mn2+ in MnCl2, Fe3+ in Fe2(NO3)3
- At higher O.S., transition elements form covalent compounds or oxoanions 1
- At high O.S., the cations are highly polarising due to high charge density
can only exist as covalent compounds (e.g. TiCl 4, V2O5) or oxoanions (e.g.
CrO42-, Cr2O72-, MnO4-)
- Generally TM ions of charges +4 and above cannot exist in aqueous solutions
- E.g. Vanadium exists in aqueous solutions as V 2+ or [V(H2O)6]2+ ion. Once it is
oxidised to the +4 or +5 oxidation state, it exists as VO 2+ or VO2+ in water
respectively
- The Cr3+ ions can be found in aqueous solution but once this ion is oxidised to
Cr(VI), it exists as either CrO42- or Cr2O72- ion in water
- Nature of
- O.S.
- Example
Oxide
- Low
- Ionic
- MnO (+2) + H2SO4 MnSO4 + H2O
- +2, +3
- Basic
- Intermedia
- Amphoteric
- Cr2O3 (+3) + 2NaOH + 3H2O
1 Refers to chemical compounds with the generic formula A xOyz-

te
- +4
- High
- +5, +6,
+7
-

Covalent
Acidic

Mn2O7

(+7)+

2NaOH 2NaMnO4 + H2O

Relative Stabilities of oxidation states of transition elements in


terms of E
-

2NaCr(OH)4
Cr2O3 + 3H2SO4 Cr2(SO4)3 + 3H2O

Relative Stabilities of oxidation states of transition elements are reflected


by standard electrode potential E
The more positive the E value, the more likely the forward reaction i.e.
reduction will occur

Trend: Relative stability of +2 O.S. w.r.t. +3 O.S. increases across the


transition element series (except Fe and Cr)
-

shown by E of M3+ (aq) + e M2+, more positive higher tendency to

reduce to M2+
-

Note:
i. Accurate data for the chart is necessarily incomplete since Sc2+, Cu3+
and Zn3+ do not exist and Ni3+ is not stable in aqueous solution
ii. E data for Sc, Cu and Zn included in the chart have been estimated
from ionisation energy and hydration energy data
Anomaly: The E value for Fe3+(aq)/Fe2+(aq) is more negative than the E
value for Mn3+(aq)/Mn2+(aq)
Oxidation of M2+ to M3+ involves the removal of 3rd electron from 3d orbital
Trend is broadly similar to that of third ionisation energies M2+ (g) M3+(g),
including dip from Mn to Fe
Removal of 3rd electron from d6 system of Fe2+ is easier due to interelectronic
repulsion between 3 electrons occupying the same d-orbital
Fe2+ is a stronger reducing agent than expected (prefers to be oxidised, i.e.
exist as Fe3+)
Anomaly: The E value for Cr3+(aq)/Cr2+(aq) is more negative than

the E value for V3+(aq)/V2+(aq)

- Break in trend is not reflected in the general trend for third
Cr2+
ionisation energies



Cr3+

Under presence of H2O ligands, d orbitals are split into 2 groups of different
energy
Removal of 3rd electron from d4 system of Cr2+ is easier since the electron
removed is from a higher energy group
Cr2+ is thus a stronger reducing agent than expected

Oxidation Abilities

Compounds of TM with high O.S. tend to have oxidising properties


indicated by presence of high +ve E values

Reducing Abilities
TM in elemental states generally have reducing properties, reducing ability
decreases across the row
Low/negative E values of M2+ (aq)/M (s) systems

E generally becomes less negative/more positive


reduction from M2+ to M becomes more likely
reduction from M to M2+ becomes less likely from element to elemnet
thus reducing acility of transition metal generally decreases

- Complexes
-

Complex Formation

Complex formed when a metal ion or atom forms dative covalent or


coordinate bonds with surrounding ions or molecules called ligands
Ligand Neutral or anions which possess at least 1 unshared pair of
electrons used to form a coordinate bond with the central metal atom/ion
Reason:
Transition metal cations have
I.
Vacant low-lying orbitals (e.g. 3d, 4s, 4p orbitals)
ii.
High charge density able to attract molecules or anions (ligands)
that are rich in electrons.
- Able to attract molecules or anions (ligands) that are rich in electrons to
form dative bonds in its vacant orbitals
Metal cation acts as lone pair acceptor (Lewis acid) and ligands as lone
pair donors (Lewis base)
- Lone pair from each ligand occupies energetically accessible vacant orbital
on the central transition ion to form a dative covalent/coordinate bond

Features of a complex

1. Net Charge on Complex


- Sum of oxidation state or charge on metal ion and the charge on the
ligands
- Net Charge = O.S. of Metal Ion + Charge on Ligands (either neutral or
negative)
- E.g. [CuCl4]2-, [Cu(NH3)4(H2O)2]2+
2. Coordination Number
- Defined as no. of dative bonds formed between ligands and the central metal
atom or ion
- Cu2+ ions coordination no. of 6 with H2O, but 4 with Cl- Different metal ions may show different coordination number with the same
ligand

Types of Ligands

Classified based on number of atoms


May be neutral or negatively charged ions
May be some atoms with lone pairs in the ligand that do not donate to the
central metal atom or ion e.g. ethanedioate ion
-

Monodentate

Bidentate

2 atoms in each ligand binds to


metal

3 atoms in each ligand binds to


metal

:Cl-, :OH-, -:CN, H2O:,


:NH3, :CO

1 atom in the ligand binds to


metal

H2N:CH2CH2:NH2
- C2O42-

Tridentate
-

DETA:
-

Hexadentate

6 atoms in each ligand bind to


metal

EDTA
-

Monodentate

Only one atom in a monodentate ligand binds to the metal


No. of coordinate bonds formed between metal and each ligand=1
Common monodentate ligands
-

Ligand

Type

Name

Bidentate

Only one atom in a monodentate ligand binds to the metal


No. of coordinate bonds formed between metal and each ligand=2
Common bidentate ligands
-

Ligand

Type

Name

structure

Nature of complexes

Complexes can be neutral, cationic or anionic

Net charge on complex = (O.S. or charge on metal ion) + (total charge on


ligands)

Net charge>0 cationic


Net charge=0 neutral
Net charge<0 anionic

Shapes of Complex Ions

1. Coordination No. = 2: Linear


2. Coordination No. = 4: Tetrahedral or Square
Planar
3. Coordination No. = 6: Octahedral
- Coordinati - Coordinati - examples on
on
number
geometry
- 2
- Linear
-

Tetrahedr
al

Square
planar

shape

Octahedra
l

Complex Chemistry

Colour of Complexes

Transition metal complexes are usually coloured both in the solid state and in
solution
-

C
o
2

H2O
Pink
Soln
[Co(
H2O)
2+
6]

OH-

Blue/green Ppt

[Co(H2O)4(OH)2]

C
r
3

Violet
Soln
[Cr(H
3
2O)6]

C
u
2

F
e
3
+

L.
Blue
Soln
[Cu(
H2O)
2+
6]
Pale
Yello
w
Soln
[Fe(H
3
2O)6]

CO32-

Pink
Ppt
CoCO3

Green
ppt
[Cr(H2O
)3(OH)3]

L.
Gre
en
Soln
[Cr(
OH)
36]

L. Blue Ppt
[Cu(H2O)4{OH)2]

Green Soln
[Cr(NH3)6]3+

F
e

Pale
Gree

Others

- Dark
Blue Soln
- [Cu(NH3)4
(H2O)2]2+
[Cu(NH3)4
]2+

Blue/gr
een
Ppt
CuCO3

Yellow
[CuCl4]2-

Brown Ppt

[Fe(H2O)3(OH)3]

Brown
Ppt
Efferve
scence
[Fe(H2
O)3(OH
)3]

2+

NH3 (2)
YellowishBrown
Soln
[Co(NH3)6]

Dark Green Ppt

[Fe(H2O)4(OH)2]

Dark
Green
Ppt

Deep
/Blood
Red
[Fe(H2O)
2+
5(SCN)]
- Red
[Fe(CN)6
]3+
- Yellow
[Fe(CN)6]4

2 Under dilute NH3 (aq) conditions, ligands will be OH. Under concentration NH3
conditions, ligands will be NH3

2
+

n
Soln
[Fe(H
3
2O)6]

FeCO3

M
n 2
+

Pink
Soln
[Mn(
H2
2O)6]
+

N
i
2
+

Blue
Soln
[Ni(N
H3)6]2

Blue Soln
[Ni(NH3)6]2
+

Explanation of Colour of Complex


Isolated transition metal ions has 5 degenerate 3d orbitals, all
with same energy
When transition metal ions are surrounded by ligands, d-orbitals
are split into 2 groups of different energy levels3

When white light shines onto the complex, an electron in the d orbital of
lower energy level is promoted to an empty or partially-filled d orbital
of higher energy, undergoing d-d electronic transition
During the transition, the d electron absorbs a quantum of light of certain
wavelength from the visible region of the electromagnetic spectrum
The colour observed is then the colour of transmitted light, which is a
mixture of remaining wavelengths that have not been absorbed
Complementary Colours
E.g.
Y
Explanation
G
O
of Colour of If a color is absorbed, the main color of the transmitted light is the other color
B
Cu2+ (aq)
R
V
Blue
In aqueous solutions, each Cu2+ ion is surrounded by 6 H2O ligand in an
octahedral complex, [Cu(H2O)6]2+
H2O ligands split the d orbitals of Cu2+ (aq) ions into 2 groups of energy levels
Cu2+ (aq) ions undergo the following energy transition when they absorb light:

3 Electrons in d-orbitals and those in ligand repel each other, hence d-orbitals
closer to ligands will have a higher energy than those further away which results
in d-orbitals splitting in energy

The ions will absorb visible light of a certain energy level corresponding to the
energy gap (red)
Colour observed is the colour of transmitted light, blue, which is the
complement of the colour absorbed
Factors Affecting Colours
Depends on the energy gap E between the two groups of d-orbitals. It
depends on

Absence of colour in Sc(III), Zn(II) and Cu(I) compounds is due to


either no d electrons or a completely filled d subshell, hence
dd transition is not possible
Higher the O.S., the larger the d-d orbital splitting larger E
- Nature and
shorter
O.S. of Metal
o Fe2+ (aq) Green (red absorbed), Fe 3+ (aq) Yellow (violet
absorbed)
o Cr2+ (aq) Blue (orange absorbed), Cr3+ (aq) Violet (yellow
absorbed)
To absorb light, a metal ion must possess at least 1 d electron
and an empty or partially filled d-orbital in higher energy
level
- No. of d
o Sc3+ compounds are not coloured [Ar]3d04s0 no dElectron
electron for dd transition
o Cu+/Zn2+ compounds are not coloured [Ar]3d104s0 all d
orbitals are completely filled with electrons no dd
transition
Splitting pattern of d orbitals
depend on shape of complex ion,
which results in different energy
gaps between high and low
- Shape of
Complex Ion energy groups
Different wavelength of absorbed
light

Different ligands split the d orbitals to a different extent


different energy gaps between high and low energy groups
amount of energy absorbed by d electron during dd transition
differs
A stronger field ligand causes a larger split in d orbitals larger
Nature of
energy gap lower absorbed light of longer transmitted
Ligand Ion
- Strength of Ligands:
(large ) I- < Br- < SCN- < Cl- < F- < -OH < C2O42- H2O < NCS- <
NH3 < NO2- < CN- CO (small )
2+
[Fe(H2O)6] - pale green (red absorbed)
[Fe(CN)6]4- - yellow
(violet absorbed)
Cu(I) is colourless
Oxidation state is +1
Electronic configuration of Cu(I) is
3d orbitals of Cu(I) is completely

- Cu(III) is coloured
- Oxidation state is +3
- Electronic configuration of Cu(III) is 1s
- Cu(III) has empty d orbitals which
allow d d electronic transitions to

filled.
d d electronic transitions cannot
occur.

occur.
Colour observed is the colour of
transmitted light, which is a
mixture of remaining wavelengths
that are not absorbed.

Ligand Exchange

Stronger ligand can displace a weaker ligand from a complex ion during
ligand exchange
Weaker ligands can also displace a stronger ligand if the weaker ligand is of
high concentrations
If ML6 + Y ML5Y + L Y is a stronger ligand than L, replacing L in ML 6 to
form a more stable complex
E.g. Conc. HCl when added to Cu2+ (aq), solution changes from blue to green

Cl- ions in high concentrations displaces H2O ligands in the blue [Cu(H2O)6]2+
complex to form yellow [CuCl4]2- complex: [Cu(H2O)6]2+ (aq) + 4Cl- (aq) [CuCl4]2(aq) + 6H2O (l)
Presence of both blue [Cu(H2O)6]2+ and yellow [CuCl4]2- complex ions give the
solution a green colour
Ligand exchange for oxyhaemoglobin, carbaminohaemoglobin and
carboxyhaemoglobin

CO2 ligand can be displaced by O2 to form oxy-haemoglobin in a reversible


reaction, allowing haemoglobin to carrying oxygen from one part of the body
to another
- CO2/O2 ligand can also be replaced irreversibly by a stronger CO ligand, which
prevents O2 molecule from binding to the Fe2+ ion in haemoglobin to form
oxyhaemoglobin toxic CO and CN- Anhydrous CuSO4 (white) dissolves readily. Describe and explain observations
when anhydrous CuSO4 is stirred with water, followed by addition of NH 3 (aq)
until in excess
- Pale blue solution is formed Formation of [Cu(H 2O)6]2+ complex ions
- CuSO4 (s) + 6H2O [Cu(H2O)6]2+ (aq) + SO42- (aq)
- Pale blue precipitate forms when NH3 is added Formation of
[Cu(H2O)4(OH)2](s)
- (1): [Cu(H2O)6]2+ (aq) + 2OH- [Cu(H2O)4(OH)2] + 2H2O, where OHreplaces H2O as ligands
- Deep blue solution is in excess NH3 formation of [Cu(NH3)4(H2O)2]2+
- (2): [Cu(H2O)6]2+ (aq) + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O, where stronger
NH3 ligands replaces weaker H2O ligands to form a deep blue complex
- Decreases concentration of [Cu(H2O)6]2+ in solution. By LCP, equilibrium (1)
shifts left to increase concentrations of [Cu(H 2O)6]2+ (aq) precipitate
dissolves

- Catalyst
-

A substance that

Increases the rate of reaction by providing an alternative pathway with


lower activation energy and itself remaining chemically unchanged at
the end of a reaction.
Provides an alternative pathway of lower activation energy for the
reaction to occur

Types of catalyst: Heterogeneous catalyst, Homogenous catalyst

Heterogeneous catalyst

- The catalyst and reactants are in different physical states/ phase


- Usually, the catalyst is solid and the reactants are liquid or gases, and
the rate-determining step occurs on the solid surface
- Heterogeneous catalyst is also known as surface catalysis
- The catalyst provides sites, usually termed active sites, at which
reaction can occur
- Its catalytic action is thought to work in 3 stages:
1. Adsorption
2. Reaction
3. Desorption
- Transition elements and their compounds are extensively used as
catalysts in many industrial processes
-

Process

Haber process ammonia


production
Hydrogenation of alkenes
Contact process sulphuric acid
production
Why are transition metals and their compounds
catalysts?

Catal
yst

good heterogeneous

- A transition metal has partially filled d subshell and d electrons


- The vacant low lying d orbitals can accept electron pairs form
reactant molecules
- The d electrons can be used to form temporary bonds (e.g. van
der Waals forces) with reactant molecules that have adsorbed
onto the catalyst surface
-

Activation energy is lowered and the rate of reaction is increased in


several possible ways:

o Adsorption weakens the bonds in reactant molecules and


allows these bonds to break more readily, thereby lowering
the activation energy
o Adsorption of reactant molecules alongside each other
increases the surface concentration of reactants
o Reactant molecules that are adsorbed onto the surface are
more likely to undergo collisions with in-coming reactant
molecules
o Reactant molecules are held on the catalyst surface with the
correct orientation for reaction to occur
Product molecules form and desorb from catalyst surface

Homogenous catalyst
-

both the catalyst and reactants are in the same physical state/phase
Transition metals are good homogenous catalysts because they
have the ability to exist in various oxidation states
This facilitates the formation of intermediate via alternative reaction
pathways that require lower activation energies
Its catalytic action is thought to work in 2 stages:

- The catalyst reacts with reactant and is converted into an


intermediate
- Intermediate undergoes reaction to yield the product and the
catalyst is regenerated.
- Takes part in the reaction by providing an alternative pathway with
lower activation energy by first forming an intermediate which is
later consumed in the reaction
- Examples:
-

Oxidation of I- by S2O82- (aq) with Fe3+ as catalyse

The reaction is kinetically slow due to high activation energy, Ea


(repulsion between two negatively charge ions, I- and S2O82-)
Fe3+ ion catalyses the reaction by providing an alternative
pathway with a lower activation energy via the intermediate
Fe2+
Reaction involves a reaction between oppositely charged ions,
which attract each other, resulting in lower Ea

Step 1: Fe3+ oxidises I- to I2 and Fe2+ intermediate is formed

Step 2: Fe2+ reduces S2O82- to SO42- and Fe3+ is regenerated:

Overall reaction is faster

Activation energy is lowered as both steps involve collisions between


two oppositely charged ions