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41 views31 pages

D Block

Uploaded by

alokranjansharma11
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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D BLOCK ELEMENTS

● D-block elements are often called as ‘transition elements because


their position in periodic table is between the s-block and p-block
elements.

● A transition element may be defined as the element whose atom


in ground state or ion in one of common oxidation states, has
partly filled d-sub shell i.e. having electrons between 1 to 9.

● The general electronic configuration of d-block elements is (n–1)


d1–10 ns0–2, where n is the outermost shell.
General Trends of Transition Elements

1) METALLIC CHARACTER

● Nearly all the transition elements display typical metallic properties


such as high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre.

● Most transition elements have ccp/hcp type structures.


● The transition elements are very much hard and have low volatility,
they have high enthalpy of atomisation.

● Cr, Mo and W have maximum number of unpaired electrons and


therefore, these are very hard metals and have maximum enthalpies
of atomisation in their respective period.

● The metals of the 4d and 5d series have greater enthalpies of


atomisation than the corresponding elements of the 3d and this is an
important factor indicating for the occurrence of much more frequent
metal-metal bonding in compounds of the heavy transition metals
2) MELTING AND BOILING POINT

● Melting and boiling point of d-block > s-block


Reason : Stronger metallic bond formed present by unpaired
d-electrons.

● In Zn, Cd, and Hg there is no unpaired electron present in d-


orbital, hence due to absence of covalent bond melting and
boiling point are very low in series. (Volatile metals Zn, Cd, Hg).

● In 3d series Sc to Cr melting and boiling point increases then


Mn to Zn melting and boiling point decreases.
● Mn and Tc have comparatively low melting point, due to weak
metallic bond because of stable Half filled (d5 ) configuration
and high IP
● Lowest melting point Hg (– 38°C) ;
● Highest melting point W ( 3400°C )
3) DENSITY

● The atomic volumes of the transition elements are low compared


with the elements of group 1 and 2. Therefore the densities of the
transition metals are high.
● Across a period from left to right atomic volumes decrease and
atomic masses increase. Hence the densities also increase across
a period.
Sc ≤ Ti ≤ V ≤ Cr ≤ Mn ≤ Fe ≤ Co ≤ Ni ≈ Cu > Zn
(Zinc is an exception having large atomic volume and hence lower
density)

● 3d < 4d << 5d
● Maximum Density : Ir > Os
COLOR OF COMPOUNDS
4) OXIDATION STATE

● The transition metals exhibit a large number of oxidation states.


With the exception of a few elements, most of these show
variable oxidation states. These different oxidation states are
related to the electronic configuration of their atoms .

● In general oxidation state of d-block element is given as


minimum oxidation state = number of 's' electrons
maximum oxidation state = number of 's' electrons + unpaired
'd' electron .

● Higher oxidation state in d-block = +8 (Os, Ru)


● On moving in a period stability of higher oxidation state
decreases

● On moving down the group stability of higher oxidation state


increases
5) ELECTRODE POTENTIAL
TRENDS IN STABILITY OF HIGHER OXIDATION
STATES

● The transition elements react with halogens at high temperatures


to form transition metal halides. The halogens react in the
following decreasing order ; F2 > Cl2 > Br2 > I2

● Since fluorine is the most electronegative element, the transition


metals show highest oxidation states with fluorine. The highest
oxidation states are found in TiX4 (tetrahalides, X = F, Cl, Br and
I), VF5 and CrF6 .

● The +7 oxidation state for Mn is not shown by simple halides.


However, MnO3 F is known in which the oxidation state of Mn is
+7.

● The tendency of fluorine to stabilise the highest oxidation state is


due to either higher lattice enthalpy as in case of CoF3 or higher
bond enthalpy due to higher covalent bonds e.g., VF5 and CrF6
Copper in +2 oxidation state is more stable than in +1 oxidation
state. This can be explained on the basis of much larger negative
hydration enthalpy of Cu2+ (aq) than Cu+ , which is much more
than compensates for the large energy required to remove the
second electron i.e., second ionisation enthalpy of copper
TRENDS IN STABILITY OF HIGHER OXIDATION STATES

● The ability of oxygen to stabilize the highest oxidation state is


demonstrated in their oxides.

● It may be noted that the ability of oxygen to stabilise these high


oxidation states exceeds that of fluorine. For example, manganese
forms highest fluoride as MnF4 whereas the highest oxide is Mn2O7
. This is due to the fact oxygen has great ability to form multiple
bonds to metals.

● The transition elements in the +2 and +3 oxidation states mostly


form ionic bonds whereas with higher oxidation states, the bonds
are essentially covalent e.g., in MnO4 – all bonds are covalent. As
the oxidation number of a metal increases, the ionic character of
their oxides decrease.
For example, in case of Mn, Mn2O7 is a covalent. In these higher
oxides the acidic character is predominant.
7) MAGNETIC PROPERTIES
8) FORMATION OF INTERSTITIAL COMPOUNDS

● Transition metals form interstitial compounds with elements


such as hydrogen, boron, carbon and nitrogen.
● The small atoms of these non-metallic elements (H, B, C, N,
etc.) get trapped in vacant spaces of the lattices of the
transition metal atoms
Eg : WC , Fe₃C , TiH₁.₃₀₋₁.₈₀

PROPERTIES
● They are generally non-stoichiometric compound.
● Neither typical ionic nor covalent.
● Harder then pure metal
● High melting point then pure metal
● Malleability and ductility less than pure metal
● Chemical inert
9) ALLOY FORMATION

● Alloys are homogeneous solid solutions in which the atoms


of one metal are distributed randomly among the atoms of the
other metal.
● The alloys are generally formed by those atoms which have
metallic radii within about 15% of each other.
● Transition metals form a large number of alloys.
● The transition metals are quite similar in size and therefore
the atoms of one metal can substitute the atoms of other
metal in its crystal lattice

Note : Fe, Co, Ni do not form amalgam with Hg (Due to large


difference in size)
COMPOUNDS OF D-BLOCK ELEMENTS

KMnO₄
● This is the most important and well known salt of permanganic
acid and is prepared from the pyrolusite ore .
● It is prepared by fusing pyrolusite ore either with KOH or
K₂CO₃
In presence of atmospheric oxygen.
2MnO₂ + 4KOH + O₂ --------> 2K₂MnO₄ + 2H₂O
2MnO₂ + 2K₂CO₃ + O₂ --------> 2K₂MnO₄ + 2CO₂

The solution is now treated with a current of chlorine or ozone or


carbon dioxide to convert manganate into permanganate .
Effect of heating : On strongly heating, it decomposes with
liberating oxygen.

2K₂Cr₂O₇ --------> 2K₂CrO₄ + Cr₂O₃ + 3/2O₂

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