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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
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
Transition Elements
Formation of Cations
-
Transition Elements
- Physical Properties
-
trend
explan
ation
Atomic radii
Transition Elements
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
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
s-block elements
-
Transition Elements
elements
trend
- Increases significantly
explan - 1st IE involves the removal of
ation
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
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
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 elemnts
-
Transition elemnets have higher first ionisation energies than s-block metals
of the same period
Across TE,
Transition Elements
- 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
Transition Elements
s-block elements
s-block elements
- Low
Transition elements
- Very high
Tre
nd
Re
aso
n
Trend: transition elements have higher m.p. and b.p. than s-block elementsss
Tre
nd
Re
aso
n
s-block elements
- Generally Lower
-
Transition elements
- generally higher
-
Transition Elements
electrons
delocalised 3d and 4s
valence electrons
Mechanical properties
Calcium
- Copper
- Very good conductor
- Both 4s and inner 3d electrons are
- Good conductor
- Inner shell electrons are not available for
available for delocalisation due to
delocalisation as they are very different
their proximity in energies
Note:
not all 3d electrons are
in energies from the valence electrons
- Fewer electrons are available to conduct
delocalised and used in conduction
- More electrons are available to
current/heat
conduct a current/heat
- Chemical properties
-
Elem
ent
Electronic
Configuration
Oxidation State
Transition Elements
Ca
Sc
Ti
[Ar]4s2
[Ar]3d14s2
[Ar] 3d24s2
[Ar] 3d34s2
Cr
[Ar] 3d54s1
Mn
[Ar] 3d54s2
Fe
[Ar] 3d64s2
Co
[Ar] 3d74s2
Ni
Cu
Zn
[Ar] 3d84s2
[Ar] 3d104s1
[Ar] 3d104s2
- +2
- +3
+1, +2, +3, +4
+1, +2, +3, +4,
+5
+1, +2, +3, +4,
+5, +6
+1, +2, +3, +4,
+5, +6, +7
+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 lowr 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
Transition Elements
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
- Intermediat
- Cr2O3 (+3) + 2NaOH + 3H2O 2NaCr(OH)4
e
- Amphoteric
- Cr2O3 + 3H2SO4 Cr2(SO4)3 + 3H2O
- +4
- High
- Covalent
- Mn2O7 (+7)+ 2NaOH 2NaMnO4 + H2O
- +5, +6, +7
- Acidic
-
Trend: Relative stability of +2 O.S. w.r.t. +3 O.S. increases across the transition
element series (except Fe and Cr)
-
reduce to M2+
-
note:
Transition Elements
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
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
Cr3+
Transition Elements
- Complexes
-
Complex Formation
Features of a complex
Types of Ligands
Monodentate
Bidentate
H2N:CH2CH2:NH2
- C2O42-
Tridentate
-
DETA:
-
Transition Elements
Hexadentate
EDTA
-
Monodentate
Ligand
Type
Name
Bidentate
Ligand
Type
Name
structure
Nature of complexes
shape
Transition Elements
number
2
geometry
Linear
Tetrahedr
al
Square
planar
Octahedra
l
Complex Chemistry
Colour of Complexes
Transition metal complexes are usually coloured both in the solid state and in
solution
-
C o
H 2O
Pink
Soln
OH-
Blue/green Ppt
[Co(H2O)4(OH)2]
NH3 (2)
- YellowishBrown Soln
-
CO32-
Pink
Ppt
Others
-
Transition Elements
[Co(
H2O)6
]2+
C r
3
Violet
Soln
[Cr(H2
O)6]3+
Green
ppt
[Cr(H2O)
3(OH)3]
L.
Gree
n
Soln
[Cr(
OH)6
]3-
L.
Blue
Soln
- [Cu(
H2O)6
]2+
C
u
2
+
[Co(NH3)6]2
L. Blue Ppt
[Cu(H2O)4{OH)2]
CoCO3
Green Soln
[Cr(NH3)6]3+
Dark Blue
Soln
[Cu(NH3)4
(H2O)2]2+
[Cu(NH3)4
]2+
Blue/gr
een Ppt
CuCO3
Yellow
[CuCl4]2-
F
e
3
+
Pale
Yellow
Soln
[Fe(H2
O)6]3+
Brown Ppt
Brown
Ppt
Efferve
scence
[Fe(H2O
)3(OH)3]
[Fe(H2O)3(OH)3]
Deep
/Blood
Red
[Fe(H2O)5
(SCN)]2+
- Red
[Fe(CN)6]
3+
Pale
Green
Soln
2
- [Fe(H2
+
O)6]3+
- Pink
M
Soln
n - [Mn(
2
H+
2
O)
2
6]
F
e
N
i
2
+
Blue
Soln
- [Ni(N
H3)6]2+
[Fe(H2O)4(OH)2]
Dark
Green
Ppt
FeCO3
Yellow
[Fe(CN)6]4-
Blue Soln
[Ni(NH3)6]2
+
2 Under dilute NH3 (aq) conditions, ligands will be OH. Under concentration NH3
conditions, ligands will be NH3
Transition Elements
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
Y
G
If a colourBis absorbed, the main colour of the transmitted light is the other colour
R
V
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 dorbitals splitting in energy
Transition Elements
Nature of
Ligand Ion
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
Transition Elements
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