The D-Block

The d block:
The d
series
block consists of three horizontal

in periods 4, 5 & 6
10 elements in each series

Chemistry is different from other
elements
Special electronic configurations important
Differences within a group in the d block are
less sharp than in s & p block
Similarities across a period are greater
SS CI 11.5 The d bloc

1
Electronic Configuration
Across the 1st row of the d block
(Sc to Zn) each element
has 1 more electron and 1 more proton

Each additional electron enters the
3d sub-shell
The core configuration for all the
period 4 transition elements is that of
Ar
1s22s22p63s23p6

2
Energy
4p
3d
4s
3p
3s
2p
2s
1s
Ar
1s2 2s2 2p6 3s2 3p6

3
Energy
4p
3d
4s
3p
3s
2p
2s
1s
Sc
1s2 2s2 2p6 3s2 3p6 3d1 4s2
4
Electronic Arrangement
Element Z
3d
4s
Sc
21
[Ar]
Ti
22
[Ar]
23
[Ar]
Cr
24
[Ar]
Mn
25
[Ar]
Fe
26
[Ar]
Co
27
[Ar]
Ni
28
[Ar]
Cu
29
[Ar]
Zn
30
[Ar]

5
Chromium and Copper

Cr and Cu dont fit the pattern of
building up the 3d sub-shell, why?
In the ground state electrons are always
arranged to give lowest total energy
Electrons are negatively charged and repel
each other
Lower total energy is obtained with e- singly
in orbitals rather than if they are paired in
an orbital
Energies of 3d and 4s orbitals very close
together in Period 4
6
Chromium and Copper

At Cr
Orbital energies such that putting one

e- into each 3d and 4s orbital gives
lower energy than having 2 e- in the
4s orbital
At Cu
Putting 2 e- into the 4s orbital would

give a higher energy than filling the
3d orbitals
7
Energy
4p
3d
4s
3p
3s
2p
2s
1s
Cr
1s2 2s2 2p6 3s2 3p6 3d5 4s1
8
Energy
4p
3d
4s
3p
3s
2p
2s
1s
Cu
1s2 2s2 2p6 3s2 3p6 3d10 4s1
9
What is a transition metal?

Transition metals [TMs] have
characteristic properties
e.g. coloured compounds, variable oxidation
states
These are due to presence of an inner

incomplete d sub-shell
Electrons from both inner d sub-shell
and outer s sub-shell can be involved in
compound formation
10

Not all d block elements have
incomplete d sub-shells
e.g. Zn has e.c. of [Ar]3d104s2, the
Zn2+ ion ([Ar] 3d10) is not a typical TM
ion
Similarly Sc forms Sc3+ which has the
stable e.c of Ar. Sc3+ has no 3d
electrons
11

For this reason, a transition metal
is defined as being an element
which forms at least one ion with a
partially filled sub-shell of d
electrons.
In period 4 only Ti-Cu are TMs!

Note that when d block elements form
ions the s electrons are lost first
12
What are TMs like?

TMs are metals
They are similar to each other but
different from s block metals eg Na and
Mg
Properties of TMs
Dense metals
Have high Tm and Tb
Tend to be hard and durable
Have high tensile strength
Have good mechanical properties

13
What are TMs like?

Properties derive from strong metallic
bonding
TMs can release e- into the pool of mobile
electrons from both outer and inner shells
Strong metallic bonds formed between the
mobile pool and the +ve metal ions
Enables widespread use of TMs!
Alloys very important: inhibits slip in crystal
lattice usually results in increased hardness
and reduced malleability

14
Effect of Alloying on TMs

15
TM Chemical Properties
Typical chemical properties of the

TMs are
Formation of compounds in a variety of
oxidation states
Catalytic activity of the elements and
their compounds
Strong tendency to form complexes
See CI 11.6
Formation of coloured compounds

See CI 11.6

16
Variable Oxidation States

TMs show a great variety of
oxidation states cf s block metals
If compare successive ionisation
enthalpies (Hi) for Ca and V as
follows
M(g)
M+(g)
M2+(g)
M3+(g)
M+(g) + eM2+(g) + eM3+(g) + eM4+(g) + e-
Hi(1)
Hi(2)
Hi(3)
Hi(4)

17
Hi for Ca and V
Ionisation Enthalpies
Element
[kJ mol-1]
Hi(1) Hi(2) Hi(3) Hi(4)
Ca [Ar]4s2
+596 +1152 +4918 +6480
V [Ar]3d34s2
+656 +1420 +2834 +4513

18
Hi for Ca and V
Both Ca & V always lose the 4s electrons
For Ca
Hi(1) & Hi(2) relatively low as corresponds
to removing outer 4s e Sharp increase in Hi(3) & Hi(4) cf Hi(2)
due to difficulty in removing 3p e-
For Sc
Gradual increase from Hi(1) to Hi(4) as
removing 4s then 3d eSS CI 11.5 The d bloc
19
Oxidation States of TMs

In the following table
Most important OSs in boxes
OS = +1 only important for Cu
In all others sum of Hi(1) + Hi(2)
low enough for 2e- to be removed
OS = +2, where 4s e- lost shown by
all except for Sc and Ti
OS = +3, shown by all except Zn
20

S
c
+3
Ti
C
r
M
n
F
e
C
o
N
i
C
u
Z
n
+2
+2
+2
+2
+2
+2
+2
+2
+3
+3
+3
+3
+3
+3
+3
+3
+4
+4
+1
+4
+5
+6
+6
+7
+6

21

No of OSs shown by an element
increases from Sc to Mn
In each of these elements highest OS is

equal to no. of 3d and 4s e-
After Mn decrease in no. of OSs shown

by an element
Highest OS shown becomes lower and less
stable
Seems increasing nuclear charge binds 3d emore strongly, hence harder to remove

22

In general
Lower OSs found in simple ionic

compounds
E.g. compounds containing Cr3+, Mn2+, Fe3+,

Cu2+ ions
TMs in higher OSs usually covalently

bound to electronegative element such
as O or F
E.g VO3-, vanadate(V) ion; MnO4-,
manganate(VII) ion
Simple ions with high OSs such as V5+ &
Mn7+ are not formed

23
Stability of OSs
Change from one OS to another is a
redox reaction
Relative stability of different OSs
can be predicted by looking at
Standard Electrode Potentials
E values

24
Stability of OSs
General trends
Higher OSs become less stable
relative to lower ones on moving from
left to right across the series
Compounds containing TMs in high OSs
tend to be oxidising agents e.g MnO4 Compounds with TMs in low OSs are
often reducing agents e.g V2+ & Fe2+

25
Stability of OSs
General trends (continued)
Relative stability of +2 state with respect to
+3 state increases across the series
For compounds early in the series, +2 state
highly reducing
E.g. V2+(aq) & Cr2+(aq) strong reducing agents
Later in series +2 stable, +3 state highly

oxidising
E.g. Co3+ is a strong oxidising agent, Ni3+ & Cu3+ do
not exist in aqueous solution.

26
Catalytic Activity
TMs and their compounds effective and
important catalysts
Industrially and biologically!!
The people in the know believe
catalysts provide reaction pathway with lower

EA than uncatalysed reaction (see CI 10.5)
Once again,
availability of 3d and 4s e ability to change OS

among factors which make TMs such good
catalysts
27
Heterogeneous Catalysis
Catalyst in different phase from reactants
Usually means solid TM catalyst with reactants
in liquid or gas phases
TMs can
use the 3d and 4s e- of atoms on metal

surface to from weak bonds to the reactants.
Once reaction has occurred on TM surface,
these bonds can break to release products
Important example is hydrogenation of

alkenes using Ni or Pt catalyst

28
Heterogeneous Catalysis

29
Homogeneous Catalysis
Catalyst in same phase as reactants
Usually means reaction takes place in
aqueous phase
Catalyst aqueous TM ion
Usually involves
TM ion forming intermediate compound

with ome or more of the reactants
Intermediate then breaks down to form
products
30
Homogeneous Catalysis
O
HO H C
O
C
O
C
HO H C
3 HO
OH
O +
C
2 HC
+ 4 OH2
Above reaction is that used in

Activity SS5.2
2,3-dihydroxybutanoate ion with
hydrogen peroxide
Reaction catalysed by Co2+
31
Suggested Mechanism
REACTANTS
INTERMEDIATE
H2O2 +
-
O2CCH(OH)CH(OH)C02Co2+ (pink)
Regenerated
Catalyst
Co2+ reduces
containing
H2O2 & gets

oxidised to
Co3+
Co3+ (green)
PRODUCTS
CO2, methanoate, H2O
Co2+ (pink)
Co3+ oxidises
2,3hydroxybutanoate &
gets
reduced to
Co2+

32

The D-Block

Uploaded by

Copyright:

Available Formats

The D-Block

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

The D-Block

Uploaded by

Copyright:

Available Formats

The d block:

block consists of three horizontal

10 elements in each series

SS CI 11.5 The d bloc

has 1 more electron and 1 more proton

SS CI 11.5 The d bloc

SS CI 11.5 The d bloc

SS CI 11.5 The d bloc

Chromium and Copper

Chromium and Copper

Orbital energies such that putting one

Putting 2 e- into the 4s orbital would

What is a transition metal?

These are due to presence of an inner

What is a transition metal?

What is a transition metal?

In period 4 only Ti-Cu are TMs!

What are TMs like?

SS CI 11.5 The d bloc

What are TMs like?

SS CI 11.5 The d bloc

Effect of Alloying on TMs

SS CI 11.5 The d bloc

Typical chemical properties of the

Formation of coloured compounds

SS CI 11.5 The d bloc

Variable Oxidation States

M+(g) + eM2+(g) + eM3+(g) + eM4+(g) + e-

SS CI 11.5 The d bloc

+596 +1152 +4918 +6480

+656 +1420 +2834 +4513

Oxidation States of TMs

Oxidation States of TMs

SS CI 11.5 The d bloc

Oxidation States of TMs

In each of these elements highest OS is

After Mn decrease in no. of OSs shown

SS CI 11.5 The d bloc

Oxidation States of TMs

Lower OSs found in simple ionic

E.g. compounds containing Cr3+, Mn2+, Fe3+,

TMs in higher OSs usually covalently

SS CI 11.5 The d bloc

SS CI 11.5 The d bloc

SS CI 11.5 The d bloc

Later in series +2 stable, +3 state highly

SS CI 11.5 The d bloc

The people in the know believe

catalysts provide reaction pathway with lower

availability of 3d and 4s e ability to change OS

use the 3d and 4s e- of atoms on metal

Important example is hydrogenation of

SS CI 11.5 The d bloc

SS CI 11.5 The d bloc

TM ion forming intermediate compound

Above reaction is that used in

H2O2 & gets

SS CI 11.5 The d bloc