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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
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
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
3d
4s
Formation of Cations
-
- Physical Properties
-
trend
explan
ation
Atomic radii
trend
explan
ation
S-block elements
-
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
Ionic radii
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
S-block elements
-
trend
expla
natio
n
Anomaly: zinc
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
-
Across TE,
- 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
-
Density
S-block elements
Tre
nd
Rea
son
s-block elements
- Low
-
Transition elements
- Very high
-
Trend: transition elements have higher m.p. and b.p. than s-block elements
Tre
nd
Rea
son
s-block elements
- Generally Lower
-
Transition elements
- generally higher
-
Mechanical properties
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
-
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
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
te
- +4
- High
- +5, +6,
+7
-
Covalent
Acidic
Mn2O7
(+7)+
2NaCr(OH)4
Cr2O3 + 3H2SO4 Cr2(SO4)3 + 3H2O
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
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
- Complexes
-
Complex Formation
Features of a complex
Types of Ligands
Monodentate
Bidentate
H2N:CH2CH2:NH2
- C2O42-
Tridentate
-
DETA:
-
Hexadentate
EDTA
-
Monodentate
Ligand
Type
Name
Bidentate
Ligand
Type
Name
structure
Nature of complexes
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]
[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
+
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
- 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
- Catalyst
-
A substance that
Heterogeneous catalyst
Process
Catal
yst
good heterogeneous
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: