D and F Block Elements
D and F Block Elements
INTRODUCTION
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ELECTRONIC CONFIGURATION
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ELECTRONIC CONFIGURATION OF
CHROMIUM & COPPER
The expected electronic confi guration of chromium should
be 1s2 2s2 2p6 3s2 3p6 3d4 4s2, in this the 4s subshell is
completely fi lled but 3d subshell is neither completely fi lled
or half fi lled. Due to inter electronic repulsion forces one
4s- electrons transfers to 3d subshell to acquire the observed
confi guration as 1s2 2s2 2p6 3s2 3p6 3d5 4s1.
Copper has expected electronic confi guration 1s2 2s2 2p6
3s2 3p6 3d9 4s2. The inter-electronic repulsion, forces one 4s
electron to enter 3d subshell. The observed electronic
confi guration of copper is 1s2 2s2 2p6 3s2 3p6 3d10 4s1.
There is a extra stability due to completely fi lled 3d
subshell and half fi lled 4s subshell.
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THINK AND ANSWER
Anomalous
electronic configuration in the 3d series are of
(a) Cr and Fe (b) Cu and Zn (c) Fe and Cu (d) Cr and Cu
ANS: d)
Zinc and mercury do not show variable valency like d-block
elements because
a)they are soft b)their d-shells are complete
c)they have only two electrons in the outermost subshell.
d)their d-shells are incomplete
ANS: b)
Which block of elements are known as transition elements?
(a) p-block (b) s-block (c) d-block (d) f-block
ANS: c)
Write the electronic configuration of chromium (Atomic
number;Cr=24)
ANS:[Ar]
Which one is of the following is the lightest transition element?
a) Ti b)Sc c) Fe d) Hg
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ANS: b)
GENRAL CHARACTERISTICS OF
TRANSITION ELEMENTS
i. Exhibit metallic properties such as
malleability, ductility, metallic luster etc.
ii. They involve strong metallic bonding and have
compact structure. Therefore they have high
density and high melting and boiling points.
iii. Good conductors of heat and electricity.
iv. In the transition metals (n-1) d and ns
electrons are of nearly same energy level.
Therefore most of these electrons take part in
chemical bonding. Hence they exhibit variable
oxidation states.
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vi. In the most of cations of the transition metals,
there are unpaired electrons.
vii. Form large number of complexes.
viii.Transition metals and their compounds have
catalytic property.
ix. Transition metals form organometallic
compounds.
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GENERAL TRENDS IN PROPERTIES
OF FIRST ROW ELEMENTS
Metallic Character
Nearly all transition metals have the simple
hexagonal close packed (hcp), cubic close packed
(ccp) or body centered cubic(bcc) latt ices which are
characteristic of true metals.
The hardness of these metals indicates the presence
of covalent bonds in them.
The metals such as Cr, Mo and W have maximum number
of unpaired d-electrons. Therefore, these metals are very
hard. On the other hand, Zn, Cd, Hg are not very hard
because they do not have unpaired d-electrons.
The high melting and boiling points of transition
metals are due to their close-packed structures. 12
m.p. and b.p. of
transition metals
are very high as
compared to
representative
elements.
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IONIZATION ENTHALPY
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OXIDATION STATE
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OXIDATION
STATES K2FeO4
K3Fe(CN)6
K4Fe(CN)6
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Copper(3d 1 0 4s 1 ) and zinc (3d 1 0 4s 2 ) exhibit +2 oxidation state.
Copper salts in +1 oxidation state are called cuprous salts.
Copper(I)
iodide
Copper in +2 O.S. are known
as copper or cupric salts.
CuSO4
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Highest oxidation state is +8 which shown by Os and Rn.
Osmium tetroxide
OsO4
Manganese shows +7 oxidation state.
MnO4
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ATOMIC AND IONIC RADII
IMP Give
Reason
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Q. Write two characteristics of the transition
elements.
Q. Which metal in the first transition series
(3d series) exhibits +1 oxidation state most
frequently and why? 21
COLOUR
The colour of a substance depends upon the absorption of light
of a perticular wavelength,of visible lights(400 to 800nm)
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In general colour of a transition ion can be related to
presence of unpaired d electrons
d-d transition
Nature of groups
Geometry of the complex formed by metal ions
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CATALYTIC PROPERTIES
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MAGNETIC PROPERTIES
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A paramagnetic substance is characterized by its eff ective
magnetic moment() which is given by the expression
= B.M.
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FORMULATION OF INTERSTITIAL
COMPOUNDS
Transition metals have defect in their crystal latt ice.
The transition metals form a number interstitial compounds
with elements such as hydrogen, carbon, nitrogen, boron.
The small atoms of these elements (C, N, H, B, etc.) occupy
the vacant spaces (interstices) in the latt ice of transition
metals resulting in the formation of interstitial compounds.
For example, TiC, ,N, etc.
Mn4N
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ALLOY FORMATION
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ALLOY
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FUN FACTS
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USES OF ALLOY
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CO MM ON Physical Chemical
properties properties
P R OP ER TI ES All d block
element are Electropositive
Lustrous and in nature
shining
Exhibit variable
Hard and have
valencies and
high density
form color salts.
Good reducing
Good electrical
agents and form
and thermal
insoluble
conductor
oxides.
Fe,Mo,Cu Zn
High tensile
are biological
strength and
important
mallleability
metals.
Many
Catalyse
compound are
biological
paramagnetic
reaction.
act as catalyst 33
F-BLOCK ELEMENTS -
LANTHANOIDS
The elements in which the diff erentiating electron (last
electron) enters into (n-2) f orbital are known as f-block
elements.
In all 28 elements from atomic number 58 to 71 and from 90
to 103 are collectively called f-block elements.
All these elements show intermediate behavior as compared
to electropositive and electronegative elements. Because of
periodic position and properties, these elements are also
known as inner transition elements.
There are two series of inner transition elements.
Lanthanoid series (4f block elements) and actinoid series (5f
block elements).
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A rare-earth element (REE) or rare-earth metal (REM ), as
defi ned by IUPAC, is one of a set of seventeen chemical
elements in the periodic table, specifi cally the fi fteen
lanthanides, as well as scandium and ytt rium.
Scandium and ytt rium are considered rare-earth elements
because they tend to occur in the same ore deposits as the
lanthanides and exhibit similar chemical properties.
Rare-earth elements are cerium (Ce), dysprosium (Dy), erbium
(Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum
(La), lutetium (Lu), neodymium (Nd), praseodymium (Pr),
promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb),
thulium (Tm), ytterbium (Yb) and yttrium (Y).
They are not especially rare, but they tend to occur together in
nature and are diffi cult to separate from one another.
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POSITION OF LANTHANOIDS
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ELECTRONIC CONFIGURATION OF
LANTHANOIDS
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CHEMICAL REACTIVITY OF
LANTHANOIDS
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LANTHANOID CONTRACTION AND
ITS CONSEQUENCES
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EFFECTS OF LANTHANOID
CONTRACTION
DECREASE IN BASICITY
Due to the lanthanoid contraction the size of the tripositive
lanthanoid ion (M³⁺) regularly decreases with increase in
atomic number i.e. from La³⁺ to Lu³⁺.
The ionic character of M-OH bond decrease and covalent
character of M-OH bond gradually increases.
Basicity and ionic character of hydroxides decrease in the
order of La(OH)₃ >Ce(OH)₃>………….Lu(OH)₃. This is in
accordance with Fajan’s principle. (According to this rule,
larger size of cation, greater is the tendency of such
hydroxides to dissociate and stronger will be the base).
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IONIC RADII OF POST LANTHANOIDS
The elements which follow the lanthanoids in the third
transition series are known as post lanthanoids.
This trend disappears after the lanthanoids and pairs of
elements. Zr-Hf, (group 4) Nb-Ta, (group 5) Mo-W (group
6) and Tc-Re (group 7) etc. have almost identical sizes. This
atoms possess similar number of valence electrons and
similar properties. These pairs of elements are called
`Chemical twins’.
A well known alloy of lanthanoid is misch metal.
(lanthanum metal, iron and traces of S, C, Ca, and Al). It is
used to manufacture bullets and shells. Mixed oxides are
used as catalysts.
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ACTINOIDS
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TRANSURANIC ELEMENT
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POSITION IN PERIODIC TABLE
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ELECTRONIC CONFIGURATION
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OXIDATION STATE
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QUESTIONS
Why do actinoid
show wide range
of O.S?
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