Advance Chemistry

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CHAPTER

4
The d- and f-Block
Elements
Recap Notes

TRANSITION ELEMENTS Transition series : d-block consists of four


(d-BLOCK ELEMENTS) transition series,
Elements in which the last electron enters 1st Transition series or 3d series 21Sc – 30Zn
any one of the five d-orbitals of their 2nd Transition series or 4d series 39Y – 48Cd
respective penultimate shell are known as 3rd Transition series or 5d series 57La, 72Hf
transition elements or d-block elements.  – 80Hg
Their general electronic configuration is th
4 Transition series or 6d series 89Ac, 104Rf
(n – 1)d1 – 10ns0 – 2.  – 112Cn

General characteristics :
Melting and boiling points High due to strong metallic bonding
Enthalpies of atomisation High due to strong interatomic interactions
Ionisation enthalpies Generally increases from left to right in a series
Oxidation states Variable due to participation of ns and (n – 1)d electrons
Atomic radii Decrease from left to right but become constant when pairing of
electrons takes place
Complex formation Form complexes due to high nuclear charge and small size and
availability of empty d-orbitals to accept lone pair of electrons
donated by ligands.
Coloured compounds Form coloured compounds due to d-d transitions
Magnetic properties Transition metal ions and their compounds are paramagnetic
due to presence of unpaired electrons in the (n – 1)d-orbitals
and it is calculated by using the formula, m = n(n + 2) where, n
is the no. of unpaired electrons.
Catalytic behaviour Due to variable oxidation states and ability to form complexes
Interstitial compounds Due to empty spaces in their lattices, small atoms can be easily
accommodated
Alloy formation Due to similar atomic sizes

INNER TRANSITION ELEMENTS X Actinoids : Last electron enters one of


( f-BLOCK ELEMENTS) the 5f-orbitals. Thorium (At. no. 90) to
X Lanthanoids : Last electron enters one lawrencium (At. no. 103).
of the 4f-orbitals. Cerium (At. no. 58) to General electronic configuration :
lutetium (At. no. 71). (n – 2)f 1 – 14 (n – 1)d0 – 1 ns2
70 CBSE Board Term-II Chemistry Class-12

General characteristics of lanthanoids :


Atomic and ionic Decrease on going from La to Lu.
radii
Oxidation states Most common oxidation state of lanthanoids is +3. Some elements exhibit
+2 and +4 oxidation states due to extra stability of empty, half-filled or fully-
filled f-subshell, e.g., Ce4+ acts as an oxidising agent and gets reduced to Ce3+,
Eu2+, Yb2+ act as strong reducing agents and get oxidised to Eu3+ and Yb3+.
Action of air All the lanthanoids are silvery white soft metals and tarnish readily in
moist air. They burn in oxygen of air and form oxides (Ln2O3 type).
Coloured ions They form coloured trivalent metal ions due to f-f transitions of unpaired
electrons. La3+ and Lu3+ are colourless ions due to empty (4f 0 ) or fully
(4f 14) orbitals.
Magnetic La3+, Lu3+ are diamagnetic while trivalent ions of the rest of lanthanoids
properties are paramagnetic.
Reducing agents They readily lose electrons and are good reducing agents.
Electropositive Highly electropositive because of low ionisation energies.
character

Alloy formation They form alloys easily with other metals especially iron.
Tendency to form Lanthanoids do not have much tendency to form complexes due to low
complexes charge density because of their large size. The tendency to form complexes
and their stability increases with increasing atomic number.

Lanthanoid contraction : In lanthanoid charge than screening effect hence


series, with increasing atomic number, there contraction in size occurs.
is progressive decrease in atomic/ionic radii
X Consequences : Their separation is
(M3+ ions) from La3+ to Lu3+.
difficult, they have small differences in
X Reason : Due to addition of new electrons
into f-subshell and imperfect shielding of properties and 4d and 5d transition series
one electron by another in the f-orbitals, have almost same atomic radii (Zr and Hf
there is greater effect of increased nuclear have similar properties due to same size).
The d- and f-Block Elements 79

92. Assertion : Members of 4d and 5d series Reason : The effective nuclear charge felt by
of transition elements have nearly same atomic (n – 1)d electrons is higher as compared to that
radii. by ns electrons.

Reason : Atomic and ionic radii for transition 94. Assertion : The maximum oxidation state of
chromium in its compounds is +6.
elements are smaller than their corresponding
Reason : Chromium has only six electrons in ns
s-block elements.
and (n – 1)d orbitals.
93. Assertion : In transition elements, ns 95. Assertion : Transition metals are poor
orbital is filled up first and (n – 1)d afterwards, reducing agents.
during ionization ns electrons are lost prior to Reason : Transition metals form numerous
(n – 1)d electrons. alloys with other metals.

SUBJECTIVE TYPE QUESTIONS


Very Short Answer Type Questions (VSA)
1. Give reasons for the following : 7. How would you account for the following :
Eu2+ is a strong reducing agent. Among lanthanoids, La(III) compounds are
2. Write the formula of an oxoanion of predominant. However, occasionally in solutions
manganese (Mn) in which it shows the oxidation or in solid compounds, +2 and +4 ions are also
state equal to its group number. obtained.
3. Name a member of the lanthanoid series
8. Account for the following :
which is well known to exhibit +4 oxidation state.
Zr and Hf have almost similar atomic radii.
4. Assign reason for the following :
Copper (I) ion is not known in aqueous solution. 9. Write the formula of an oxoanion of chromium
5. Name a member of the lanthanoid series (Cr) in which it shows the oxidation state equal
which is well known to exhibit +2 oxidation state. to its group number.
6. Account for the following : 10. Zn2+ salts are white while Cu2+ salts are
Zn is not considered as a transition element. coloured. Why?

Short Answer Type Questions (SA-I)


11. Why is europium (II) more stable than (ii) Which is the most stable ion in +2 oxidation
cerium (II)? state and why?
12. The magnetic moment of a transition metal 14. How would you account for the following :
ion is found to be 3.87 BM. How many number of (i) The E°M 2+/M for copper is positive (+0.34 V).
unpaired electrons are present in it ? Copper is the only metal in the first series of
transition elements showing this behaviour.
13. Use the data to answer the following and (ii) The metallic radii of the third (5d) series of
also justify giving reasons : transition metals are nearly the same as those
Cr Mn Fe Co of the corresponding members of the second (4d)
series.
E°M2+/M –0.91 –1.18 –0.44 –0.28
15. Write the electronic configuration of Ce3+
E°M3+/M2+ –0.41 +1.57 +0.77 +1.97
ion, and calculate the magnetic moment on
(i) Which is a stronger reducing agent in the basis of ‘spin-only’ formula. [Atomic no. of
aqueous medium, Cr2+ or Fe2+ and why? Ce = 58]
80 CBSE Board Term-II Chemistry Class-12

16. (i) Which metal in the first transition series oxidation states occurs in the middle of the
(3d-series) exhibits +1 oxidation state most series.
frequently and why? 18. What is lanthanoid contraction and what is
(ii) Which of following cations are coloured in it due to? Write two consequences of lanthanoid
aqueous solutions and why? contraction.
Sc3+, V3+, Ti4+, Mn2+
19. What is meant by ‘disproportionation’? Give
(At. Nos. Sc = 21, V = 23, Ti = 22, Mn = 25)
an example of a disproportionation reaction in
17. How would you account for the following :
aqueous solution.
(i) Cr2+ is reducing in nature while with the
same d-orbital configuration (d4), Mn3+ is an 20. (i) Write two characteristic of the transition
oxidising agent. elements.
(ii) In a transition series of metals, the (ii) Which of the 3d-block elements may not be
metal which exhibits the greatest number of regarded as the transition elements and why?

Short Answer Type Questions (SA-II)


21. (i) Explain the cause of paramagnetism in (ii) The E° value for the Mn3+/Mn2+ couple is
lanthanoid ions. much more positive than that for Fe3+/Fe2+
(ii) Nb and Ta exhibit similar properties. Give couple.
reason. (iii) The highest oxidation state of a metal is
(iii) Among the ionic species, Sc3+, Ce4+ and Eu2+, exhibited in its oxide or fluoride.
which one is a good oxidising agent. 27. (a) Assign reasons for the following :
22. Following are the transition metal ions of 3d (i) Cu(I) ion is not known to exist in aqueous
solutions.
series :
(ii) Transition metals are much harder than the
Ti4+, V2+, Mn3+, Cr3+
alkali metals.
(Atomic numbers : Ti = 22, V = 23, Mn = 25, Cr = 24) (b) Name the lanthanoids which show
Answer the following : abnormally low value of third ionisation enthalpy.
(i) Which ion is most stable in aqueous solution
28. Account for the following :
and why?
(i) The transition metals and their compounds
(ii) Which ion is strong oxidising agent and why? act as good catalysts.
(iii) Which ion is colourless and why? (ii) The lowest oxide of transition metal is basic,
23. Compare qualitatively the first and second the highest is amphoteric/acidic.
ionisation potentials of copper and zinc. Explain (iii) The magnetic moment (B.M.) of Fe2+ ion
the observation. is 24 .
24. (i) Ce (IV) is a good analytical reagent. 29. (a) Account the following :
Why? (i) Transition metals form large number of
(ii) Account for the following : Copper(I) complex compounds.
compounds are white whereas copper(II) (ii) E°° value for the Mn3+/Mn2+ couple is highly
compounds are coloured. positive (+1.57 V) as compared to Cr3+/Cr2+.
(iii) Which of following cations are coloured in
25. How do the oxides of transition elements in aqueous solutions and why?
lower oxidation states differ from those in higher Sc3+, V3+, Ti4+, Mn2+
oxidation states and why? (At. Nos. Sc = 21, V = 23, Ti = 22, Mn = 25)
26. How would you account for the following : 30. (i) Out of the ions Ag+, Co2+ and Ti4+ which
(i) The atomic radii of the metals of the third will be coloured in aqueous solution?
(5d) series of transition elements are virtually (ii) If each one of the above ionic species is placed
the same as those of the corresponding members in a magnetic field, how will they respond and
of the second (4d) series. why?
The d- and f-Block Elements 81

31. (a) Explain the following : (i) Why is E°(Cu2+/Cu) value exceptionally positive?
The enthalpies of atomization of transition (ii) Why is E°(Mn2+/Mn) value highly negative as
metals are quite high. compared to other elements?
(b) Explain the following observations. (b) Give reason and select one atom/ion which
(i) With the same d-orbital configuration will exhibit asked property :
(d4), Cr2+ is a reducing agent while Mn3+ is an (i) Sc3+ or Cr3+ (exhibit diamagnetic behaviour)
oxidising agent. (ii) Cr or Cu (high melting and boiling point)
(ii) There is hardly any increase in atomic size 34. Give reasons for the following :
with increasing atomic numbers in a series of (i) Mn3+ is a good oxidising agent.
transition metals. (ii) EM2+/M values are not regular for first row
32. (i) Transition metals have very high melting transition metals (3d-series).
and boiling points. Why? (iii) d-block elements exhibit more oxidation
(ii) In d-block element, ionic radii of ions of states than f-block elements.
the same charge decreases progressively with 35. How would you account for the following :
increasing atomic number in a series. Why?
(i) The oxidising power of oxoanions are in the
33. (a) order
E°(M2+/M) Cr Mn Fe Co Ni Cu VO+2 < Cr2O72– < MnO4–
 –0.91 –1.18 –0.44 –0.28 –0.25 +0.34 (ii) The third ionization enthalpy of manganese
From the given data of E° values, answer the (Z = 25) is exceptionally high.
following questions : (iii) Cr2+ is a stronger reducing agent than Fe2+.

Long Answer Type Questions (LA)


36. (a) Give reason : 38. (a) The elements of 3d transition series are
(i) Sc (21) is a transition element but Ca (20) is given as
not. Sc Ti V Cr Mn Fe Co Ni Cu Zn
(ii) The Fe2+ is much more easily oxidised to Answer the following :
Fe3+ than Mn2+ to Mn3+. (i) Write the element which shows maximum
number of oxidation states. Given reason.
(b) How would you account for the following :
(ii) Which element has the highest melting
(i) Metal-metal bonding is more extensive in point?
the 4d and 5d series of transition elements than
(iii) Which element shows only +3 oxidation
the 3d series.
state?
(ii) Mn (III) undergoes disproportionation reaction (iv) Which element is a strong oxidising agent in
easily. +3 oxidation state and why?
(iii) Co (II) is easily oxidised in the presence of (v) Why Mn2O3 is basic whereas Mn2O7 is
strong ligands. acidic?
37. Compare the general characteristics of 39. (a) Account for the following :
the first series of the transition metals with (i) Transition metals show variable oxidation
those of the second and third series metals in states.
the respective vertical columns. Give special (ii) Zn, Cd and Hg are soft metals.
emphasis on the following points : (b) Give reason :
(i) electronic configuration Iron has higher enthalpy of atomization than
(ii) oxidation states that of copper.
(iii) ionisation enthalpies and (c) What are interstitial compounds? Write their
(iv) atomic sizes. properties.

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