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D BLOCK ELEMENTS
Presented By
Dr.T.VARA PRASAD,
HOD,
Department of Chemistry,
P.R.Government College (A),
Kakinada
Synopsis:
Definition of D-Block elements
Transition elements.
General and Physical properties of elements
Atomic & Ionic size
Ionization Enthalpy
Oxidation states
Coloured ions
Catalytic properties
Magnetic properties
Formation of complex compounds
Formation of interstitial compounds
}d-block elements:
The elements of periodic table belonging
to group 3 to 12 are known as d-Block
elements. because in these elements last
electron enters in d sub shell or d orbital .
}The d -block elements lies in between s- and
p-block elements in the long form of
periodic table
Definition of d-block elements
A transition element is defined as the
one which has incompletely filled d
orbitals in its ground state or in any
one of its oxidation states. i.e.
A transition element should have
partially filled (n-1) d orbital.
Transition Elements
Group 7 Presentation
All d block elements are not transition
elements but all transition elements are d-
block elements
All d block elements are not transition
elements because d block elements like
Zinc have full d10 configuration in their
ground state as well as in their common
oxidation state.which is not according to
definition of transition elements.
How are d - Block Elements &
Transition elements different?
GENERAL & PHYSICAL PROPERTIES OF D-BLOCK ELEMENTS
Ø PHYSICAL PROPERTIES
Ø ATOMIC & IONIC SIZE
Ø IONIZATION ENTHALPY
Ø OXIDATION STATES OF D-BLOCK ELEMENTS
Ø COLOURED IONS
Ø CATALYTIC PROPERTIES
Ø MAGNETIC PROPERTIES
Ø FORMATION OF COMPLEX COMPOUNDS
Ø FORMATION OF INTERSTITIAL COMPOUNDS
ATOMIC & IONIC SIZE
Ø Along the rows nuclear charge increases but
the penultimate d-sub shell has poor shielding
effect so atomic and ionic size remain almost
same .
Ø The radii of the third (5d) series are
virtually the same as those of the
corresponding members of the second
series.
¢ This phenomenon is associated with the
intervention of the 4f orbital, the filling of
4f before 5d orbital results in a regular
decrease in atomic radii called Lanthanoid
contraction which essentially compensates
for the expected increase in atomic size with
increasing atomic number.
¢ The net resultof the lanthanoid contraction is
that the second and the third d series exhibit
similar radii (e.g., Zr 160 pm, Hf 159 pm)
IONIZATION ENTHALPIES
IE2 :V < Cr > Mn and Ni < Cu > Zn
IE3 : Fe << Mn
¢ Due to an increase in nuclear charge which
accompanies the filling of the inner d-
orbitals , There is an increase in ionization
enthalpy along each series of the transition
elements from left to right.
¢ However, many small variations occur.
• Transition elements have variable oxidation
states ,due to very small energy difference
between (n-1)d & ns sub-shell electrons from
both the sub-shell take part in bonding
oxidation states
•Low oxidation states are found when a complex
compound has ligands capable of π-acceptor character
in addition to the σ-bonding.
*For example, in Ni(CO)4 and Fe(CO)5, the oxidation
state of nickel and iron is zero.
• The elements which give the greatest number of
oxidation states occur in or near the middle of the
series. Manganese, for example, exhibits all the
oxidation states from +2 to +7.
Most of the transition metal compounds (ionic
as well as covalent) are coloured both in solid
state & in aqueous state.
Generally the elements/ions having unpaired
electrons produce coloured compound.
COLOURED IONS
Scandium
oxide
Vanadyl
Sulphate
dihydrate
Titanium
oxide sodium
chromate Potassium
ferricyanide
Nickel(II)
nitrate
hexa-
hydrate
Zinc
sulfate
Hepta-
hydrate
Mangnaese(II)
chloride
tetrahydrate
Cobalt(II)
chloride
Copper(II)
sulfate
penta-
hydrate
Splitting of d-orbital energies by an octahedral field of ligands
ES
GS
eg
t2g
hv
eg
t2g
Do
ES
GS
complex in electronic
Ground State (GS)
d-d
transition
complex in
electronic
excited state
(ES)
An artist’s wheel
CATALYTIC PROPERTIES
üVanadium(V) oxide,V2O5 (in Contact Process)
üFinely divided iron (in Haber’s Process)
üNickel (in Catalytic Hydrogenation)
üCobalt (Synthesis of gasoline)
Ø This property is due to-
Ø Presence of unpaired electrons in their
incomplete d orbitals.
Ø Variable oxidation state of transition metals.
Ø In most cases , provide large surface area with
free valencies.
iron(III) catalyses the reaction between iodide
and per sulphate ions
For example
Explanation
MAGNETIC PROPERTIES
¢ When a magnetic field is applied to substances,
mainly two types of magnetic behaviour are
observed: diamagnetism and paramagnetism.
¢ Diamagnetic substances are repelled by the applied
field while the paramagnetic substances are
attracted.
¢ Substances which are attracted very strongly are said
to be ferromagnetic.
¢ In fact, ferromagnetism is an extreme form of
paramagnetism.
¢ Most of the transition elements and their compounds
show paramagnetism.
¢ Paramagnetism arises from the presence of unpaired
electrons, each such electron have a magnetic
moment.
¢ The magnetic moment of any transition element or its
compound/ion is given by (assuming no contribution
from the orbital magnetic moment).
¢ μs = √n(n+2) BM
¢ Here n is the number of unpaired electrons
¢ The paramagnetism first increases in any transition
element series, and then decreases. The maximum
paramagnetism is seen around the middle of the series.
QUESTIONS-
¢ Q. 1: Which ion has maximum magnetic moment
(a) V3+ (b) Mn3+
(c) Fe3+ (d) Cu2+
¢ Ans: c
¢ Q.2. What is the magnetic moment of Mn2+ ion (Z=
25) in aqueous solution ?
¢ Ans.- With atomic number 25, the divalent Mn2+ ion in
aqueous solution will have d5 configuration (five
unpaired electrons).Hence, The magnetic moment, μ
is
¢ μ = √5(5 + 2) = 5.92BM
FORMATION OF COMPLEX COMPOUNDS
¢ Complex compounds are those in which the metal
ions bind a number of anions or neutral molecules
giving complex species with characteristic
properties.
¢ The transition metals form a large number of
complex compounds.
¢ A few examples are: [Fe(CN)6]3–, [Fe(CN)6]4–,
[Cu(NH3)4]2+ and [PtCl4]2–.
This property is due to the-
Ø comparatively smaller sizes of the metal ions
Ø their high ionic charges and the
Ø availability of d orbitals for bond formation.
Questionnaire:
1. What are D-Block elements?
2.Differentiate between D-Block elements and Transition
elements?
3.Explain Electronic configuration of D-block elements?
4.How are the oxidation states of these elements given and what
are they?
5.What are complex compounds? How are they formed in
transition elements? Explain with examples?
6.What are complex compounds? Explain how transition
elements can form complex compounds?
7. How can we get magnetic momentum of D-Block elements?
Explain?
Assignment:
1.Differentiate between D-Block elements and Transition
elements?
2.Explain Electronic configuration of D-block elements?
3.How are the oxidation states of these elements given and what
are they?
4.Explain the splitting of d-orbital energies by an octahedral
field of ligands?
5.Explain the catalytic properties of D-block elements?
6.What are complex compounds? How are they formed in
transition elements? Explain with examples?
THANK YOU

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D BLOCK ELEMENTS.pdf389.pdf

  • 1. D BLOCK ELEMENTS Presented By Dr.T.VARA PRASAD, HOD, Department of Chemistry, P.R.Government College (A), Kakinada
  • 2. Synopsis: Definition of D-Block elements Transition elements. General and Physical properties of elements Atomic & Ionic size Ionization Enthalpy Oxidation states Coloured ions Catalytic properties Magnetic properties Formation of complex compounds Formation of interstitial compounds
  • 3.
  • 4. }d-block elements: The elements of periodic table belonging to group 3 to 12 are known as d-Block elements. because in these elements last electron enters in d sub shell or d orbital . }The d -block elements lies in between s- and p-block elements in the long form of periodic table Definition of d-block elements
  • 5.
  • 6. A transition element is defined as the one which has incompletely filled d orbitals in its ground state or in any one of its oxidation states. i.e. A transition element should have partially filled (n-1) d orbital. Transition Elements
  • 8.
  • 9. All d block elements are not transition elements but all transition elements are d- block elements All d block elements are not transition elements because d block elements like Zinc have full d10 configuration in their ground state as well as in their common oxidation state.which is not according to definition of transition elements. How are d - Block Elements & Transition elements different?
  • 10. GENERAL & PHYSICAL PROPERTIES OF D-BLOCK ELEMENTS Ø PHYSICAL PROPERTIES Ø ATOMIC & IONIC SIZE Ø IONIZATION ENTHALPY Ø OXIDATION STATES OF D-BLOCK ELEMENTS Ø COLOURED IONS Ø CATALYTIC PROPERTIES Ø MAGNETIC PROPERTIES Ø FORMATION OF COMPLEX COMPOUNDS Ø FORMATION OF INTERSTITIAL COMPOUNDS
  • 12.
  • 13. Ø Along the rows nuclear charge increases but the penultimate d-sub shell has poor shielding effect so atomic and ionic size remain almost same . Ø The radii of the third (5d) series are virtually the same as those of the corresponding members of the second series.
  • 14. ¢ This phenomenon is associated with the intervention of the 4f orbital, the filling of 4f before 5d orbital results in a regular decrease in atomic radii called Lanthanoid contraction which essentially compensates for the expected increase in atomic size with increasing atomic number. ¢ The net resultof the lanthanoid contraction is that the second and the third d series exhibit similar radii (e.g., Zr 160 pm, Hf 159 pm)
  • 15. IONIZATION ENTHALPIES IE2 :V < Cr > Mn and Ni < Cu > Zn IE3 : Fe << Mn
  • 16. ¢ Due to an increase in nuclear charge which accompanies the filling of the inner d- orbitals , There is an increase in ionization enthalpy along each series of the transition elements from left to right. ¢ However, many small variations occur.
  • 17. • Transition elements have variable oxidation states ,due to very small energy difference between (n-1)d & ns sub-shell electrons from both the sub-shell take part in bonding oxidation states
  • 18. •Low oxidation states are found when a complex compound has ligands capable of π-acceptor character in addition to the σ-bonding. *For example, in Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and iron is zero. • The elements which give the greatest number of oxidation states occur in or near the middle of the series. Manganese, for example, exhibits all the oxidation states from +2 to +7.
  • 19. Most of the transition metal compounds (ionic as well as covalent) are coloured both in solid state & in aqueous state. Generally the elements/ions having unpaired electrons produce coloured compound. COLOURED IONS
  • 21.
  • 22. Splitting of d-orbital energies by an octahedral field of ligands
  • 23. ES GS eg t2g hv eg t2g Do ES GS complex in electronic Ground State (GS) d-d transition complex in electronic excited state (ES)
  • 25. CATALYTIC PROPERTIES üVanadium(V) oxide,V2O5 (in Contact Process) üFinely divided iron (in Haber’s Process) üNickel (in Catalytic Hydrogenation) üCobalt (Synthesis of gasoline) Ø This property is due to- Ø Presence of unpaired electrons in their incomplete d orbitals. Ø Variable oxidation state of transition metals. Ø In most cases , provide large surface area with free valencies.
  • 26. iron(III) catalyses the reaction between iodide and per sulphate ions For example Explanation
  • 27. MAGNETIC PROPERTIES ¢ When a magnetic field is applied to substances, mainly two types of magnetic behaviour are observed: diamagnetism and paramagnetism. ¢ Diamagnetic substances are repelled by the applied field while the paramagnetic substances are attracted. ¢ Substances which are attracted very strongly are said to be ferromagnetic. ¢ In fact, ferromagnetism is an extreme form of paramagnetism.
  • 28. ¢ Most of the transition elements and their compounds show paramagnetism. ¢ Paramagnetism arises from the presence of unpaired electrons, each such electron have a magnetic moment. ¢ The magnetic moment of any transition element or its compound/ion is given by (assuming no contribution from the orbital magnetic moment). ¢ μs = √n(n+2) BM ¢ Here n is the number of unpaired electrons
  • 29.
  • 30. ¢ The paramagnetism first increases in any transition element series, and then decreases. The maximum paramagnetism is seen around the middle of the series.
  • 31. QUESTIONS- ¢ Q. 1: Which ion has maximum magnetic moment (a) V3+ (b) Mn3+ (c) Fe3+ (d) Cu2+ ¢ Ans: c ¢ Q.2. What is the magnetic moment of Mn2+ ion (Z= 25) in aqueous solution ? ¢ Ans.- With atomic number 25, the divalent Mn2+ ion in aqueous solution will have d5 configuration (five unpaired electrons).Hence, The magnetic moment, μ is ¢ μ = √5(5 + 2) = 5.92BM
  • 32. FORMATION OF COMPLEX COMPOUNDS ¢ Complex compounds are those in which the metal ions bind a number of anions or neutral molecules giving complex species with characteristic properties. ¢ The transition metals form a large number of complex compounds. ¢ A few examples are: [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+ and [PtCl4]2–.
  • 33. This property is due to the- Ø comparatively smaller sizes of the metal ions Ø their high ionic charges and the Ø availability of d orbitals for bond formation.
  • 34. Questionnaire: 1. What are D-Block elements? 2.Differentiate between D-Block elements and Transition elements? 3.Explain Electronic configuration of D-block elements? 4.How are the oxidation states of these elements given and what are they? 5.What are complex compounds? How are they formed in transition elements? Explain with examples? 6.What are complex compounds? Explain how transition elements can form complex compounds? 7. How can we get magnetic momentum of D-Block elements? Explain?
  • 35. Assignment: 1.Differentiate between D-Block elements and Transition elements? 2.Explain Electronic configuration of D-block elements? 3.How are the oxidation states of these elements given and what are they? 4.Explain the splitting of d-orbital energies by an octahedral field of ligands? 5.Explain the catalytic properties of D-block elements? 6.What are complex compounds? How are they formed in transition elements? Explain with examples?