- The transition elements may be
defined as the elements whose atoms or simple ions contain at least one
partially filled d –orbitals.
- Properties of these elements that
are transitional between s & p block elements, there fore they are
called as transition elements.
- General electronic configuration
of these elements as ns1-2 (n-1)d1-10 .
- Lanthanides and actinides are
called inner transition elements.
Their general electronic configuration is ns2(n-1)d0-1
(n-2)f1-14
- Transition metals are having strong
metallic bonding due to presence of large no. of valence electrons
and greater nuclear charge. Hence
these are hard, possess high densities and high enthalpy of atomization.
- Transition elements are having high
melting and boiling points due to presence of large no. of half
filled d – orbitals which causes strong inter particle attractions.
- Ionization energy increases from left to right due to increase in the nuclear
charge, as the increased nuclear charge is partly cancelled by screening
effect there is no much increase.
- The reduction potential
values of transition elements varies irregularly because it depend up on
Enthalpy sublimation, Ionisation energy and hydration energy. All these values are irregularly
changing hence their reduction potential values are also varies
irregularly.
- Atomic and ionic radii decreases to middle and become constant in middle and at the
end it increases. The variation is
not much because increased nuclear charge is partly cancelled by screening
effect.
- Transition elements possess variable
oxidation states(o.s.) due to involvement of both ns electrons and
(n-1)d electrons in bonding. Lower
o.s is zero and highest is +8, +2 is the most common o.s.
- Transition metals forms complex
compounds due to small size, high charge density and presence of
empty d- orbitals.
- Transition elements forms colored
complexes due to d – d transition.
- The transition metals ions
generally contain one or more unpaired electrons in them and hence their
complexes are generally paramagnetic. If a metal ion does not have at least
one electron it behave as diamagnetic.
- Transition metal ions and their
compounds known to act as catalysts.
The catalytic activity of compounds is due to variable
oxidation states, and providing surface for adsorption.
- Transition metals are almost
similar size, there fore these elements can mutually substitute their
positions in their crystal lattices and forms alloys.
- Transition elements are capable of
entrapping smaller atoms of other elements such as H, C & N in the
interstitial position and the trapped atoms get bonded with transition
elements. And these compounds are
known as interstitial compounds.
Example Steel.
- Preparation of potassium
dichromate from chromite involves the following steps( in current syllabus it has been removed)
The chromite ore is
finely ground and heated strongly with molten alkali in the
presence of air.
2FeCr2O4
+ 8NaOH + 7 ½ O2 à 4Na2CrO4
+ Fe2O3 + 4H2O
The solution of sodium
chromate is filtered and acidified with dilute sulphuric acid so that
sodiumdichromate is obtained.
2NaCrO4 + H2SO4
à Na2Cr2O7
+ Na2SO4 + H2O
A calculated quatity of
potassium chloride is added to a hot oncentrated
solution of sodium
dichromate. Potassium dichromate is less soluble therefore it crystallizes out first.
Na2Cr2O7+
2KCl à K2Cr2O7
+ 2NaCl
§ In alkaline solution dichromate which is orange in colour is
converted to chromate which is yellow. The acidification reverses the reaction.( in current syllabus it has been removed)
2CrO4 2- + 2H+ à 2HCrO4- à Cr2O7 2- +
H2O (reversible)
a)It oxidizes potassium iodide to
iodine
Cr2O7
2- + 14H+ + 6I- à 2Cr3+ + 7H2O + 3I2
b)It oxidizes iron (ii) solution to
iron(III) solution
Cr2O7
2- + 14H+ + 6Fe2+ à 2Cr3+ + 7H2O + 6Fe3+
c) It oxidizes H2S
to S
Cr2O7
2- + 8H+ + 3H2S à 2Cr3+ + 7H2O + 3S
§ Pyrolusite ore is fused with alkali in the presence of air when
potassium manganate is formed.( in current syllabus it has been removed)
2MnO2 + 4KOH + O2 à 2K2MnO4
+ 2H2O
Potassium manganate is oxidized by using either CO2,
ozone or chlorine to potassium permanganate.
2K2MnO4 + Cl2 à 2KMnO4 + 2KCl
Potassium permanganate is crystallized from the solution
a)
It oxidizes iron(II)salts to iron(III) salts.
MnO4- + 8H+ + 5Fe2+ àMn2+ + 4H2O + 5Fe3+
b)It oxidizes SO2 to sulphuric acid
2MnO4- +
5SO2 + 2H2Oà 5SO4
2- + 2Mn2+ + 4H+
b) It oxidizes oxalic acid to
CO2 and H2O
2MnO4- +
16H+ + 5C2O42- à 2Mn2+ + 8H2O + 10CO2
§ Elements which have partly filled f-orbitals. There are two series of
inner transition elements. In the first series of inner transition elements the
4f orbitals are incomplete and electrons are progressively filled in these
orbitals as atomic number increases. These elements are called lanthanoids. In
the second series of transition elements the electrons are progressively filled in 5f- orbitals as
atomic no. increases. These elements are called actinoids.
§ As we move from La to Lu there is a gradual decrease in size .The
steady decrease in size from La to Lu is called lanthanide contraction. This is
due to poor shielding effect of
4f orbitals.
§ The important consequences are
1.
Similarities in the properties
of Y and heavier lanthanides .
2.
Similar atomic radii of second
and third transition series.
3.
Separation becomes difficult
4. Causes small differences in the
properties like basicity, solubility of salts,
formation of complexes, etc.
§ Colour of the salts
and ions in solution Most of
the lanthanide trivalent ions are coloured in solid as well as in the solution
phase. The ions containing x and (14 – x) electrons show the same
colour. The colour of the salts or ions is due to the f – f transition
of electrons.
REASONING QUESTIONs
1. Give two use of lanthanide compounds.
Ans. (i) Misch metal
is pyrophoric and used in gas lightness, tracer bullets and shell.
(ii) Oxides of neodymium and
praseodymium are used for making colour glasses.
2. why
the melting points of transition elements are high ?
Ans. The melting points of transition elements are
high due to the presence of strong
Intermetallic bonds and covalent bonds.
3. Why
Zn, Cd and Hg are not regarded as transition elements ?
Ans. Because they have the completely filled
d-subshell with outer electronic
configuration (n –1)d10 ns2.
4. Why is K2Cr2O7
generally preferred over Na2Cr2O7 in
volumetric analysis although both are
oxidising agents ?
Ans. Because Na2Cr2O7
is hygroscopic, hence it is difficult to prepare its standard solution for volumetric analysis, but because
of non hygroscopic nature of K2Cr2O7 its
standard solution can be prepared.
5. Write any two uses of pyrophoric
alloys.
Ans. Pyrophoric alloys contain rare earth metals and
are used in the preparation of ignition
and shells and flints for lightness.
6. Why do Zr and Hf exhibit similar
properties ?
Ans. Because of the lanthanide contraction Hf has
similar size to Zr, therefore both Zr
and Hf exhibit similar properties.
7. In the transition servies, with an
increase in atomic number the atomic radius does not change very much, why is it so ?
Ans.
In the transition series, the
effect of increasing nuclear change is partly cancelled by the increased screening effect
of the d- electrons of penultimate shell. Because of this reason, the
atomic radius does not change very much in the transition series.
8. Why is
the third ionization energy of manganese unexpectedly
high ?
Ans.
Third electron of the manganese
is removed from 3d-orbitals which have half filled configuration, thus have extra
stability. Due to this reason high enegy is required to remove third electron from Mn.
9. All scandium salts are white. Why
?
Ans.
Because they have no electron
in d-orbital, thus no d - d
transition is possible.Due to this reason all
salts of Sc3+ are white.
10. The
first ionisations energies of the 5d-transition elements are higher then those of 3d and 4 d transition elements. Why?
Ans:- Due to Lanthanoid contraction
11. Why do
the d-block elements exhibit a longer number of oxidation states than f-block elements ?
Ans.
Because the energy of
ns-electron and (n – 1) d-electrons are
nearly same, therefore, ns electrons as well as (n – 1)
d- electrons can take part in
bond formation in transition elements.In
fblock elements last electron goes to the
f-orbitals of second order outer most
shell, thus the difference between the energy of ns-electron and (n – 2)
f-electrons increases. Due to this reasons all the (n – 2) f-electrons cannot take
point in bond formation.
12. Explain
why the first ionisation energies of the elements of the
first transition series do not vary much with increasing atomic
numbers.
Ans.
With the increasing atomic
number, d-electrons add one by one in (n – 1)
shell or penultimate shell. The
screening effect of these d- electrons shield the
outer s-electrons from inward nuclear pull. The effect of the increase in
nuclear charge with the increase in atomic number is
opposed by the shielding effect of d-electrons . thus due to these counter
effect there is a very little variations in
the values of ionization
energies of first transition series.
13. Explain
why transition metals are paramagenetic ?
Ans.
The ions of transition metals
generally contain one or more unpaired
electrons hence the compounds of
transition metal are paramagnetic i.e., they are
weakly attracted by magnetic field.The
paramagnetic character is directly related to the value of
magnetic moment, m which intern depends
upon the number of unpaired electrons (n) i.e., B.M. = Ö n + (n + 2)
14. Give plausible reason for the fact that
transition metals have high enthalpy of
atomization.?
Ans.
Transition elements are
metallic in nature and form strong metallic
bonds. Moreever, they have incomplete d-orbitals,
hencey they can form covalent bonds also.
Due to these two reasons transition metals
have strong force of attraction. Therefore, they
have high enthalpy of atomization.
15. What is the effect of pH on the color of the
solution of potassium
dichromate ?
Ans.
A lower pH, the colour of the
solution is orange due to the solution is
orange due To the presence of dichromate ions
(Cr2O7 2–).
But in alkaline PH, the colour of
the solution changes to yellow
due to the conversion of dichromate ions to chromate ions.
2CrO4 2- + 2H+ ↔ 2HCrO4- ↔ Cr2O7
2- + H2O
(reversible)
16. Why
the compounds of transitions elements are coloured ?
Ans.
The colour of compounds of
transition elements depend upon the unpaired
electrons present in
d-orbitals fo transition element. If
d-orbitals are completely vacant or
completely filled the compounds will be
colourless, but if any unpaired electron is present in d-orbital, the compound will
be coloured due to
d - d transition. The unpaired electron is excited from one energy level to another energy level with
in the same d-sub- shell. For this purpose,
the energy is absorbed from visible region of radiation. The
complementary part of the absorbed light i.e., reflected light
will decide the colour of the compound.
17. Why
the transition elements act as catalyst? Give two examples.?
Ans.
(a) Transition metal
show variable oxidation states, therefore, they can from intermediate
products of difficult reactant
molecules.
(b) Transition elements are
capable to form interstitial compounds
due to which they can absorb and activates the reacting molecules.
Example:
(a) V2O5
is used for the oxidation of SO2 to SO3 in contact
process of H2SO4.
(b) Ni is
used as a catalyst in the hydrogenation of alkanes and alkynes
18. Why
transition elements form
(a) interstitial compounds and
(b) Alloys?
Ans.
(a) Interstitial compounds:
Transition elements form large number of interstitial compounds.
In these compounds
small size atoms like hydrogen, carbon, nitrogen, nitrogen, boron etc. occupy
the empty space of metal lattice. The small entrapped atom in the interstices
forms the bonds with metals due to which malleability and ductility of the
metals decrease, whereas tensile strength increases.
(b) Alloys: Transition element
forms alloys with each other
because they have
almost similar sizes. Due to similar sizes atoms of one metal in the crystal
lattice can easily take up the position of the atom of transition elements.
Alloys are more resistant to corrosion than the
constituent elements,
and usually harder with higher melting point.
19. Why
are Ni2+ compounds thermodynamically more stable than Pt2+
compounds, whilst Pt4+ compounds are relatively more stable than Ni4+
compounds?
Ans.
Thermodynamic stability of the
compounds can be judged on the basis of the magnitude of ionization energies.
The sum of the two first ionization energies of Ni2+ is lower than the sum of
first two ionization energies of Pt2+, therefore, Ni2+
compounds are more stable than Pt2+.
On the other hand, sum of first four ionization energies of Pt4+
lower than the sum of the first four ionization energies of Ni4+,
therefore, Pt4+ compounds are more stable than Ni4+.
20. Name a transition metal which does
not exhibit variation in oxidation state in its compounds?
Ans.
Zinc in its compounds shows an
oxidation state of + 2 only.
21. Why is + 2 oxidation state of
manganese (Z = 25) more stable than its + 3 oxidation state, while the
same is not true for iron (Z = 26)?
Ans.
The electronic configurations
of Mn2+, Mn3+, Fe2+ and Fe3+ are,
Mn2+:
1s2 2s2 2p6 3s2
3p6 3d 5 4s0
Mn3+:
1s2 2s2 2p6 3s2
3p6 3d 4
Fe2+:
1s2 2s2 2p6 3s2
3p6 3d 6 4s0
Fe3+: 1s2 2s2
2p6 3s2 3p6 3d 5
Due to the extra
stability of the half-filled orbitals d 5 configuration is
more stable than d 4 or d 6. Mn2+ and Fe3+
both have d 5 configuration. Therefore, Mn2+ is
more stable than Mn3+ and Fe3+ is more stable than Fe2+.
22. Of the
ions Co2+, Sc3+ and Cr3+ which ones will give
coloured aqueous solutions and how will
each of them respond to a magnetic field
and why?
(Atomic
numbers: Co = 27, Sc = 21, Cr = 24)
Ans. The electronic configurations of the given ions
are,
Co2+ : 1s2 2s2
2p6 3s2 3p6 3d7 No. of unpaired electrons = 3
Sc3+ : 1s2 2s2
2p6 3s2 3p6 3d0 No. of unpaired electrons = 0
Cr3+ : 1s2 2s2
2p6 3s2 3p6 3d3 No. of unpaired electrons = 3
Co2+ and Cr3+ ions will give
coloured aqueous solutions. Co2+ and Cr3+ are
paramagnetic, and Sc3+ is diamagnetic. Therefore, Co2+
and Cr3+ ions will get attracted to the magnetic field, whereas
Sc3+ ion will be repelled by the magnetic field.
23. Why is
it that anhydrous copper (II) chloride is a covalent while anhydrous copper (II)
fluoride is ionic in nature?
Ans.
This is because in halides of
transition metals, the ionic character decreases with increase in atomic mass of the halogen.
Fluorine being the most electronegative, forms ionic
salt with copper. Cupric chloride
consists of infinite chains consisting of bridging Cl atoms and has a
covalent character.
24. (a)
Assign reason for each of the following:
(i) Ce3+ can be easily
oxidised to Ce4+.
(ii) E° for Mn3+/Mn2+
couple is more positive than for Fe3+/Fe2+.
(iii) Transition metals exhibit higher
enthalpies of atomization.
(iv) The transition elements form
interstitial compounds.
(b) Mention two uses of potassium
permanganate in the laboratory. (Atomic number: Mn = 25, Fe = 26, Ce = 58)
Ans. (i) Ce3+ has only one electron
in its 4f orbitals. Due to extra stability of completely empty orbitals
belonging to an energy level as compared to having only one
electron in it, Ce3+ tends to lose its only electron
from 4f orbital and get oxidised
to Ce4+.
(ii) Mn3+
has a 4d configurtion, so it has
greater tendency to accept one electron
to acquire d 5 configuration. On the other hand, Fe3+
has a d5
configuration which is more stable than the6d`6 configuration of
Fe2+. As a result, reduction of Fe3+ to Fe2+
is not favoured. Since, E° values
reflect the reduction tendency, therefore, E° value for Mn3+/Mn2+ couple is
more positive than Fe3+/Fe2+.
(iii)
Transition metals exhibit high enthalpies of atomisation. This is because the atoms in these elements are held together
by strong metallic bonds. The metallic bond is formed as a result of
interaction of electrons in the outermost
shells. In general, greater the number of valence electrons stronger is the metallic bond.
(iv) The transition metals
form a number of interstitial compounds
in which small atoms of light elements
such as,
H, C and N occupy the voids in their lattices. The products
obtained in this way are hard and rigid. For example,
steel and cast iron become hard due to the formation of
an interstitial compound with carbon.
(b) The uses of potassium permanganate in the
laboratory are
(i) As an oxidising agent,
(ii) In volumetric estimation of reducing agents such
as
Fe2+ salts, oxalic acid etc.
25. Name a transition element which does not exhibit
variable oxidation state?
Ans:- Scandium ( Z = 21) does not exhibit variable
oxidation state.
26. Why is Cr+2reducing and Mn+3
oxidising when both have d4 configuration?
Ans:- Cr+2 is reducing as its
configuration changes from d4 to d5, the latter having a
half filled t2g level. On the other hand the change from Mn+2
to Mn+3 results in the half – filled (d5) configuration
which has extra stability.
27. How would you account for the increasing oxidizing
power in the series VO2+ < Cr2O72-‑ <
MnO4-?
Ans:-
This is due to the increasing stability of the lower species to which they are reduced.
28. How would you account for the irregular variation of ionization
enthalpies (first and second ) in the first series of
the transition elements?
Ans:- Irregular variation of ionization
enthalpies is mainly attributed to varying
degree of stability of different 3d configurations
(e.g. d0, d5, d10 are exceptionally stable.
29. In the series Sc(Z=21) to Zn (Z=30) the enthalpy of atomization
of zinc is the lowest i.e. 126kJ/mol, why?
Ans:- In the
formation of metallic bonds, no electrons from
3d- orbitals are involved in case of
zinc, while in all other metals of
the 3d series, electrons from the d-orbitals are always involved in the formation of metallic
bonds.
30. Which is a stronger reducing agent Cr+2 or
Fe+2?
Ans:- Cr+2 is stronger
reducing agent than Fe+2 Because d4 à d3 occurs in case of
Cr+2 to Cr+3 but d6 à d5 occurs in case of
Fe+2 to Fe3+. In a
medium (like water) d3 is more stable as compared to d5.
31. Why is the highest
oxidation state of a metal exhibited in its oxide or fluoride only?
Ans:- Because of small size and high electronegativity oxygen or fluorine can oxidize the
metal to its highest oxidation state.
32. What is meant by disproportionation of an oxidation
state? Give an example? Ans:- When a particular oxidation state
becomes less stable relative to other
oxidation states, one lower, one higher, it is said to undergo disportionation. For
example, manganese(VI) becomes unstable
relative to Manganese(VII) and manganese (IV) in acidic solution.
MnVIO42- +
4H+ à 2MnVIIO4- + MnIVO2 + 2H2O
33. Explain why Cu+ ion is not stable in aqueous
solution?
Ans:-
Cu+ in aqueous solution undergoes disproportionation i.e.,
2Cu+(aq.)
à Cu+2(aq.) + Cu(s),
The E0 value for this is favourable.
34.
Name a member of the lanthanoid series which is well known to exhibit +4
oxidation state?
Ans:- Cerium (Z = 58)
35.
Actinoid contraction is greater from element to element than lanthanoid
contraction. Why?
Ans:- The 5f electrons are more effectively shielded from nuclear charge, In other words
the 5f electrons themselves provide poor shielding from element to
element in the series.