Ch.8.
d and f block elements
Assignment questions.
April 1 st week
1..Why Mn and Tc has low melting point?.
Manganese and technetium have exactly half filled d-orbitals. Hence the electronic
configuration is stable. Electrons are held tightly by the nucleus so that the
delocalisation is less and metallic bond is much weaker than the preceding element.
2..Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their+3
state?
Sol: Electronic configuration of Mn2+ is 3d5. This is a half-filled configuration and hence
stable. Therefore, third ionization enthalpy is’very high, i. e., third electron cannot be lost
easily. Electronic configuration of Fe2+ is 3d6. It can lose one electron easily to achieve
a stable configuration 3d5.
3. Explain briefly how+2 state becomes more and more stable in the first half of
the first row transition elements with increasing atomic number?
Sol: Here after losing 2 electrons from j-orbitals, the 3d-orbital gets gradually occupied
with increase in atomic number. Since the number of unpaired electrons in 3d orbital
increases, the stability of the cations (M2+) increases from Sc2+ to Mn2+.
4. To what extent do the electronic configurations decide the stability of oxidation
states in the first series of the transition elements? Illustrate your answer with
examples.
Sol: In the first series of transition elements, the oxidation states which lead to exactly
half-filled or completely filled d-orbitals are more stable. For example, Mn (Z = 25) has
electronic configuration [Ar] 3d5 4 s2. It shows oxidation states + 2 to + 7 but Mn (II) is
most stable because of half-filled configuration [Ar] 3d5. Similarly Sc3+ is more stable
then Sc+ and Fe3+ is more stable than Fe2+ due to half filled it f-orbitals
5.. Why does copper not replace hydrogen from acids?
Answer:Copper does not replace hydrogen from acids because Cu has a positive E∘ value, i.e., it is
less reactive than hydrogen, which has an electrode potential of 0.0 V. So, Cu replace hydrogen
from acids.
6.. Although +3 oxidation states is the characteristic oxidation state of lanthanides but cerium
shows +4 oxidation state also. Why?
Answer:
After losing one more electron, Ce3+ acquires a stable 4f0 electronic configuration. Thus, although
the +3 oxidation state is the characteristic oxidation state of lanthanoids, cerium shows a +4
oxidation state.
7.. Explain why does colour of KMnO4, disappear when oxalic acid is added to its solution in
acidic medium.
Answer:
KMnO4 acts as an oxidising agent. It oxidises oxalic acid to CO2 and changes to Mn2+ ion, which is
colourless.
8.. When orange solution containing Cr2O72- ion is treated with an alkali, a yellow solution is
formed and when H+ ions are added to yellow solution, an orange solution is obtained.
Explain why does this happen?
Answer:
The following reaction takes place when Cr2O72- is treated with an alkali,
(orange) Cr2O72- + OH– → 2CrO42- (yellow)
When the yellow solution is treated with an acid, we get back the orange solution
(yellow) 2CrO42- + 2H+ → Cr2O72– (orange) + H2O
This reaction is reversible under proper conditions.
9.. A solution of KMnO4 on reduction yields either a colourless solution or a brown
precipitate or a green solution depending on pH of the solution. What different
stages of the reduction do these represent and how are they carried out?
Answer:
Oxidising behaviour of KMnO4 depends on the pH of the solution.
In an acidic medium (pH < 7),
MnO4– + 8H+ + 5e− → Mn2+ + 4H2O
In an alkaline medium (pH > 7),
MnO4– + e− → MnO42-
In a neutral medium (pH = 7),
MnO4– + 2H2O+ 3e− → MnO2 + 4OH−
10.. The second and third rows of transition elements resemble each other much
more than they resemble the first row. Explain why?
Answer:
Due to lanthanoid contraction, the atomic radii of the second and third-row transition elements are
almost identical. So, they resemble each other much more than first-row elements.
Assignment questions.
April 2 nd week
11.What may be the stable oxidation state of the transition element with the
following electronic configurations in the ground state of their atoms: 3d 3,3d5, 3d8
and 3d4?
Sol: (a) 3d3 4s1 = + 5.
(b) 3d5 4s2 = + 2, + 7,3d5 4s1 =+6.
(c)3d84s2 = + 2.
(d)3d44s2 = 3d5 4s1 = + 6(and + 3).
12.. Name the oxometal anions of the first series of the transition metals in which
the metal exhibits the oxidation state equal to its group number.
Sol: Cr2072- and Cr042- (Group number = Oxidation state of Cr = 6).
Mn04– (Group number = Oxidation state of Mn = 7).
13. What is lanthanoid contraction? What are the consequences of lanthanoid
contraction?
Sol: Lanthanoid Contraction : In the lanthanoids , the electrons are getting filled in the
4f-subshell. On moving from left to right, the nuclear charge increases and this increase
is expected to be compensated by the increase in the magnitude of shielding effect by
the 4 f- electrons However,
the f-electrons have very poor shielding effect. Consequently, the atomic and ionic radii
decrease from left to right and this is knwon as lanthanoid contraction.
Consequences of lanthanoid Contraction
(a)Separation Lanthanoids: All the lanthanoids have quite similar properties and due to
this reason they are difficult to separate.
(b)Variation in basic strength of hydroxides: Due to lanthanoid contraction, size of M 3+
ions decreases and thus there is a corresponding increase in the covalent character in
M—OH bond. Thus basic character of oxides and hydroxides decreases from La(OH)3
to Lu(OH)3.
(c)Similarity in the atomic sizes of the elements of second and third transition series
present in the same group. The difference in the value of atomic radii of Y and La is
quite, large as compared to the difference in the value of Zr and Hf. This is because of
the lanthanoid contraction.
(d)Variation in standard reduciton potential: Due to lanthanoid contraction there is a
small but steady increase in the standard reduction potential (E°) for the reduction
process.
M3+ (aq) + 3e– —–> 4 M(aq)
(e)Variation in physical properties like melting point, boiling point, hardness etc.
14. Why are E- values for Mn, Ni and Zn more negative than expected?
Answer:
The metals will quickly lose their electrons and get oxidised. A negative E value means that the
oxidised species is more stable than the reduced species. Here, Mn2+ (3d5) and Zn2+ (3d10) have
half-filled and fully filled d orbitals, giving them stability and, therefore, prefer to stay that way and not
get reduced. Ni2+ (3d8) has very high negative hydration enthalpy, balanced by first and second
ionisation enthalpy.
15. Why is the first ionisation enthalpy of Cr is lower than that of Zn?
Answer:
Ionisation enthalpy of Cr is less than that of Zn because Cr has a stable configuration. In the case of
zinc, the electron comes out from wholly filled 4s orbital. So, the removal of an electron from zinc
requires more energy as compared to chromium.
16. E0 of Cu is + 0.34V while that of Zn is – 0.76V. Explain.
Answer:
High ionisation enthalpy to transform Cu(s) to Cu2+ (aq) is not balanced by its hydration enthalpy.
However, in case of Zn, after removing electrons from 4s-orbital, a stable 3d 10 configuration is
acquired. Thus, value of E0 of Cu is + 0.34V while that of Zn is – 0.76V.
17. The halides of transition elements become more covalent with increasing
oxidation state of the metal. Why?
Answer:
As the oxidation state increases, the size of the ion of the transition element decreases. As per
Fajan’s rule, as the size of metal ions decreases, the covalent character of the bond formed
increases. Therefore, the halides of transition elements become more covalent with the increasing
oxidation state of the metal.
18. While filling up of electrons in the atomic orbitals, the 4s orbital is filled before
the 3d orbital but reverse happens during the ionisation of the atom. Explain
why?
Answer:
Atomic orbitals are filled in order of increasing energies. Since the energy of 3d orbital is more than
4s orbital, based on the (n+l) rule, it is filled after 4s orbital. But during ionisation, electrons in the
outermost orbital are lost. Since 4s will be the outermost orbital, in this case, electrons from this
orbital will be ionised first.
19. Reactivity of transition elements decreases almost regularly from Sc to Cu.
Explain.
Answer:
Reactivity of transition elements decreases almost regularly from Sc to Cu due to the regular
increase in ionisation enthalpy.
20. Identify A to E and also explain the Identify A to E and also explain the reactions involved.
Answer:
Compound A to D are,A = Cu B = Cu(NO3)2 C = [Cu(NH3)4] D = CO2
CuCO3 → CuO + CO2
2CuO + CuS → 3Cu + SO2
Cu + 4HNO3 (conc) →Cu(NO3)2 + 2NO +2H2O
Cu2+ + NH3 → [Cu(NH3)4]
Ca(OH)2 + CO2 → CaCO3 + H2O
CaCO3 + H2O + CO2 → Ca(HCO3)2
Assignment questions.
April 3 rd week
21.What are the characteristics of the transition . elements and why are they
called transition elements? Which of the d-block elements may not be regarded
as the transition elements?
Sol: General characteristics of transition elements.
(i)Electronic configuration – (n -1) d1-10 ns1-2
(ii)Metallic character – With the exceptions of Zn, Cd and Hg, they have typical metallic
structures.
(iii)Atomic and ionic size-ions of same charge in a given series show progressive
decrease in radius with increasing atomic number.
(iv)Oxidation state-Variable; ranging from+2 to +7.
(v)Paramagnetism – The ions with unpaired electrons are paramagnetic.
(vi)Ionisation enthalpy – Increases with increase in charge.
Formation of coloured ions – Due to presence of unpaired electrons.
(viii) Formation of complex compounds – Due to small size and high charge density of
metal ions.
(ix)They possess catalj^c properties – Due to
their ability to adopt multiple oxidation states. .
(x)Formation of interstitial compounds.
(xi)Alloy formation.
They are called transition elements due to their incompletely filled d-orbitals in ground
state or in any stable oxidation state and they are placed between s and p- block
elements. Zn, Cd and Hg have fully filled d- orbitals in their ground state hence may not
be regarded as the transition elements.
22. In what way are the electronic configuration of the transition elements
different from non-transition elements?
Sol: Electronic configuration of transition elements : (n – 1)d1-10 ns1-2. Electronic
configuration of non-transition elements : ns1-2 or ns2np1-6. From comparison, it is quite
evident that the transition elements have incomplete d-orbitals (s- orbitals in some
cases) while the non-transition elements have no d-orbitals present in the valence shells
of their atoms. This is responsible for the difference in the characteristics of the
elements belonging to these classess of elements.
23. What are the different oxidation states exhibited by the lanthanoids?
Sol: Lanthanides exhibits + 2, + 3 and + 4 oxidation states. The most common oxidation
state of lanthanoids is +3.
24. Transition elements show high melting points. Why?
Answer:The high melting points of transition metals are due to the involvement of a greater number
of electrons of (n-1)d in addition to the ns electrons in the interatomic metallic bonding.
25. When Cu2+ ion is treated with KI, a white precipitate is formed. Explain the reaction with
the help of a chemical equation.
Answer:When Cu2+ ion is treated with KI, it produces Cu2I2 white precipitate in the final product.
2Cu2+ + 4I− → Cu2I2 (White ppt.) + I2
(In this reaction, CuI2 is formed, which, being unstable, dissociates into Cu2I2 and I2 ).
26.. When a chromite ore (A) is fused with sodium carbonate in free excess of air
and the product is dissolved in water, a yellow solution of compound (B) is
obtained. Aftertreatment of this yellow solution with sulphuric acid, compound
(C) can be crystallised from the solution. When compound (C) is treated with KCI,
orange crystals of compound (D) crystallise out. Identify A to D and also explain
the reactions.
Answer:
Compound A to D are,
A = FeCr2O4 B = Na2CrO4 C = Na2Cr2O7.2H2O D = K2Cr2O7
4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
27. When an oxide of manganese (A) is fused with KOH in the presence of an
oxidising agent and dissolved in water, it gives a dark green solution of
compound (B). Compound (B) disproportionates in neutral or acidic solution to
give purple compound (C). An alkaline solution of compound (C) oxidises
potassium iodide solution to a compound (D) and compound (A) is also formed.
Identify compounds A to D and also explain the reactions involved.
Answer:
Compound A to D are,
A = MnO2, B = K2MnO4, C = KMnO4, D = KIO3
When Manganese dioxide (A) is fused with KOH, it gives a green solution of potassium manganate
(B).
2MnO2 (A) + 4KOH + O2 → 2K2MnO4 (B) +2H2O
Potassium manganate disproportionates to give purple potassium permanganate (C).
3MnO42- + H+ → 2MnO4– (C) + MnO2 + 2H2O
Potassium permanganate reacts with KI to give potassium iodate (D) and manganese dioxide.
2MnO4– + H2O + KI → 2MnO2 + 2OH– + KIO3 (D)
28. On the basis of Lanthanoid contraction, explain the following
(i) Nature of bonding in Lu2O3 and La2O3
(ii) Trends in the stability of oxo salts of lanthanides from La to Lu.
(iii) Stability of the complexes of lanthanides.
(iv) Radii of 4d and 5d block elements
(v) Trends in acidic character of lanthanide oxides.
Answer:
(i) Due to lanthanide contraction, size reduces. With the size reduction, the covalent character
increases. Therefore, Lu2O3 is more covalent than La2O3 .
(ii) Oxosalts contain oxygen as an anion. As the size of the cation reduces from La to Lu, according
to Fajan’s rules, the polarising power of the cation will increase, and it will distort the cloud of
oxygen(anion) significantly. Thus the bond weakens, and the stability also reduces.
(iii)As the size of the central atom reduces, the stability of the complex increases. A small metal ion
with a greater charge attracts the ligands better.
(iv) In 5d block elements, the effective nuclear charge increases due to poor shielding of f orbitals,
thereby reducing the size. This is called lanthanide contraction. So, the radii of 4d and 5d block
elements end up being very similar.
(v) From La to Lu, the acidic character increases. As the size reduces from La to Lu, the ability to
lose electrons(Lewis base character) reduces, so the acidity increases.
29.(a) Answer the following questions:
(i) Which element of the first transition series has the highest second ionisation
enthalpy?
(ii) Which element of the first transition series has highest the third ionisation
enthalpy?
(iii) Which element of the first transition series has the lowest enthalpy of
atomisation?
(b) Identify the metal and justify your answer.
(i) Carbonyl M(CO)5
(ii) MO3F
Answer:
1. (i) Cu, because the electronic configuration of Cu is 3d10. So, the second electron needs to
be removed from the completely filled d-orbital, which is very difficult.
(ii) Zinc, because of the electronic configuration of Zn = 3d104s2 and Zn2+=3d10, which is fully filled
and is very stable. Removal of the third electron requires very high energy.
(iii) Zinc, as it has completely filled 3d subshell, and no unpaired electron is available for metallic
bonding.
1. (i) It is Fe(CO)5 by EAN rule.
According to the EAN rule, the effective number of metal in a metal carbonyl is equal to the atomic
number of nearest inert gas EAN is calculated as
EAN = number of electrons of meta (+2) × (CO)
= atomic number of nearest inert gas
In M(CO)5 = x + 2 × (5) = 36 (Kr is the nearest inert gas)
x = 26 (atomic number of metal)
So, the metal is Fe (iron).
(ii) MO3F is MnO3F
In MO3F, let us assume M=x.
x + 3×(−2) + (−1)
x = +7
M is in a +7 oxidation state so that the given compound is MnO3F.
30. Mention the type of compounds formed when small atoms like H, C and N get
trapped inside the crystal lattice of transition metals. Also give physical and
Chemical characteristics of these compounds.
Answer:
The compounds formed when tiny atoms of H, C or N get trapped inside the crystal lattice of metals
are known as interstitial compounds. The transition metals form several interstitial compounds.
Transition metals react with hydrogen, carbon, nitrogen, boron etc., to form interstitial compounds.
Physical and Chemical properties of Interstitial Compounds
1. These compounds have very high melting points, higher than the parent transition metals.
2. These compounds are very hard. The hardness of some borides is comparable to that of a
diamond.
3. The conductivity exhibited by them is similar to their parent metal.
4. These compounds are chemically inert.
Assignment questions.
April 4 th week
31. Explain giving reasons:
(i)Transition metals and many of their compounds show paramagnetic behaviour.
(ii)The enthalpies of atomisation of the transition metals are high.
(iii)The transition metals generally form coloured compounds.
(iv)Transition metals and their many compounds act as good catalyst
Sol: (i) Magnetic properties: Transition elements and many of their compounds are
paramagnetic, i.e., they are weakly attracted by a magnetic field. This is due to the
presence of unpaired electrons in atoms, ions or molecules. The paramagnetic
character increases as the number of . unpaired electrons increases. The paramagnetic
character is measured in terms of magnetic moment and is given by
μ=√n(n+2)
where n – number of unpaired electrons.
(ii) Because of large number of unpaired electrons in d-orbitals of their atoms they have
stronger interatomic intefactions and hence stronger metallic bonding between atoms
resulting in higher enthalpies of atomisation.
(iii) Formation of coloured compounds (both in solid state as well as in aqueous
solution) is another very common characteristics of transition metals. This is due to
absorption of some radiation from visible light to cause d-d transition of electrons in
transition metal atom. The d-orbitals do not have same energy and under the influence
of ligands, the d-orbitals split into two sets of orbitals having different energies; transition
of electrons can take place from one set of d-orbitals to another set within the same
sub-shell. Such transitions are called d-d transitions. The energy difference for these d-
d transitions fall in the visible region. When white light is incident on compounds of
transition metals, they absorb a particular frequency and remaining colours are emitted
imparting a characteristic colour to the complex. Zn2+ and Ti4+ salts are white because
they do not absorb any radiation in visible region.
(iv)Catalytic properties: Many of transition metals and their compounds act as catalyst in
variety of reactions, e.g., finely divided iron in manufacture of NH3 by Haber’s process,
V2O5 or Pt in manufacture of H2S04 by Contact process, etc.). The catalytic activity is
due to following two reasons.
(a)The ability of transition metal ion to pass ” easily from one oxidation state to another
and thus providing a new path to reaction with lower activation energy.
(b)The surface of transition metal acts as very good adsorbent and thus provides
increased concentration of reactants on their surface causing the reaction to occur.
32. What are interstitial compounds? Why are such compounds well known for
transition metals?
Sol: Transition metals form large number of interstitial compounds. They are able to
entrap small atoms of elements like H, G, N, B, etc., in their crystal lattice and even can
make weak bonds with them.
Due to formation of interstitial compounds, their malleability and ductility decreases and
tensile . strength increases. Steel and cast iron are hard in comparison to wrought iron
due to the presence of trapped carbon atoms in interstitial spaces.
33. How is the variability in oxidation states of transition metals different from
that of the non-transition metals? Illustrate with examples.
Sol: The transition metals show a number of variable oxidation states due to the
participation of (n – 1) d electrons in addition to ns electrons in the bond formation. They
therefore, exhibit a large number of variable oxidation states. On the other hand, the
non-transition metals generally belonging to s-block do not show variable oxidation
states because by the loss of valence s-electrons, they acquire the configuration of the
nearest noble gas elements.
In the p-block the lower oxidation states are favoured by the heavier members (due to
inert pair effect), the opposite is true in the groups of d-block. For example, in group 6,
Mo(VI) and W(VI) are found to be more stable than Cr(VI). Thus Cr(VI) in the form of
dichromate in acidic medium is a strong oxidising agent, whereas MoO3 and WO3 are
not.
34. Out of Cu2Cl2 and CuCl2, which is more stable and why?
Answer:
CuCl2 is more stable than Cu2Cl2. The stability of Cu2+ (aq) is more than Cu+ (aq) due to the much
more negative ΔhydH∘ of Cu2+ (aq) than Cu+ (aq).
35. When a brown compound of manganese (A) is treated with HCl it gives a gas
(B). The gas taken in excess, reacts with NH to give an explosive compound (C).
Identify compounds A, B and C.
Answer:When brown compound Mn3O4 is treated with HCl, it gives chlorine gas.
Mn3O4 + 8HCl → 3MnCl2 + 4H2O + Cl2↑
Chlorine gas taken in excess reacts with ammonia to give an explosive compound NCl 3.
NH3 + 3Cl2 (excess) → NCl3 + 3HCl
The compounds A, B and C are A = Mn3O4 , B = Cl2 gas , C = NCl3 .
36.. (a) Transition metals can act as catalysts because these can change their
oxidation state.How does Fe(III) catalyse the reaction between iodide and
persulphate ions?
(b) Mention any three processes where transition metals act as catalysts.
Answer:
(a) The reaction between iodide and persulphate ions.
2I− + S2O82− → I2 + 2SO42−
We can explain this catalytic action as:
2Fe3+ + 2I− → 2Fe2+ + I2
2Fe2+ + S2O82− → 2Fe3+ + 2SO42−
(b) (i) Vanadium (V) oxide in the contact process for the oxidation of SO 2 to SO3.
(ii) Finely divided iron in Haber’s process in converting N2 and H2 to NH3.
(iii) MnO2 in preparation of oxygen from KClO3.
37.. A violet compound of manganese (A) decomposes on heating to liberate
oxygen and
compounds (B) and (C) of manganese are formed. Compound (C) reacts with
KOH in the presence of potassium nitrate to give compound (B). On heating
compound (C) with conc. H2SO4 and NaCl, chlorine gas is liberated and a
compound (D) of manganese along with other products is formed. Identify
compounds A to D and also explain the reactions involved.
Answer:
Here,
A = KMnO4
B = K2MnO4
C = MnO2
D = MnCl2
KMnO4 → K2MnO4 + MnO2 + O2
MnO2 + KOH + O2 → 2K2MnO4 + 2H2O
MnO2 + NaCl + H2SO4 → MnCl2 + 2NaHSO4 + 2H2O + Cl2
38. Describe the preparation of potassium dichromate from iron chromite ore.
What is the effect of increasing pH on a solution of potassium dichromate?
Sol: Potassium dichromate is prepared from chromate, which in turn is obtained by the
fusion of chromite ore (FeCr2O3) with sodium or potassium carbonate in free excess of
air. The reaction with sodium carbonate occurs as follows:
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to
give a solution from which orange sodium dichromate, Na2Cr,07.2H20 can be
crystallised.
Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with potassium chloride.
Orange crystals of potassium dichromate crystallise out. The chromates and
dichromates depending upon pH of the solution. If pH of potassium dichromate is
increased it is converted to yellow potassium chromate.
39. Describe the oxidising action of potassium dichromate and write the ionic
equations for its reaction with:
(i)iodide
(ii)iron (II) solution and
(iii)H2S
Sol: K2Cr207is a powerful oxidising agent. In dilute sulphuric acid medium the oxidation
state of Cr changes from+6 to + 3. The oxidising action can be represented as follows:
40. Describe the preparation of potassium permanganate. How does the acidified
permanganate solution react with (i) iron (ii) S02 and (iii) oxalic acid? Write the
ionic, equations for the reactions.
Sol: Potassium permanganate (KMn04) is prepared by the fusion of a mixture of
pyrolusite (Mn02),potassiufn hydroxide and oxygen, first green coloured potassium
manganate is formed. 2MnO2 + 4KOH + 02 —> 2K2Mn04+2H20 The potassium
manganate is extracted by water, which then undergoes disproportionation in neutral or
acidic solution to give potassium permanganate.
April 5 th week
41.For M2+/M and M3+/M2+ systems the E° values
for some metals are as follows:
Cr2+/Cr –> -0.9 V
Mn2+/Mn –> -1.2V
Fe2+/Fe –> -0.4 V
Cr3+/Cr2+ –> -0.4 V
Mn3+/Mn2+ –>+ 1.5V
Fe3+/Fe2+ –>+ 0.8V
(ii)the ease with which iron can be oxidised as compared to a similar process for
either chromium or manganese metal.
Sol: (i) Cr3+/Cr2+ has negative reduction potential. Hence, Cr3+ cannot be reduced to
Cr2+. Mn3+/Mn2+ has a large positive reduction potential. Hence, Mn3+ can be easily
reduced to Mn2+. Fe3+/Fe2+ has small positive reduction potential. Hence, Fe3+ is more
stable than Mn3+ but less stable than Cr3+.
(ii)From the E° values, the order of oxidation of the metal to the divalent cation is : Mn >
Cr > Fe.
42.. Predict which of the following will be coloured in aqueous solution?
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+, Co2+.
Sol: Only those ions will be coloured which have incomplete d-orbitals. The ions with
either empty or filled d-orbitals are colourless. Keeping this in view, the coloured ions
among the given list are :
Ti3+(3d1), V3+(3d2), Mn2+(3d5), Fe3+(3d5), Co2+ (3d7)
Sc3+ (3d°) and Cu+ (3d10) ions are colourless.
43.Compare the stability of +2 oxidation state for the elements of the first
transition series.
Sol: In general, the stability of +2 oxidation state in first transition series decreases from
left to right due to increase in the sum of first and second ionisation energies. However
Mn2+ is more stable due to half filled d-orbitals (3d5) and Zn2+ is more stable due to
completely filled d-orbitals (3d10).
44. Ionisation enthalpies of Ce, Pr and Nd are higher than Th, Pa and U. Why?
Answer:
Ce, Pr and Nd are lanthanoids and have an incomplete 4f shell, while Th, Pa and U are actinoids
and have an incomplete 5f shell.
When 5f-orbitals begin to be occupied, they will penetrate less into the inner core of electrons. The
5f-electrons will, therefore, be more effectively shielded from the nuclear charge than the 4f
electrons of the corresponding lanthanoids.
Therefore, outer electrons are less firmly held and are available for bonding in the actinoids.
45.. Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite
difficult to separate them. Why?
Answer:
Separation of Zr and Hf is pretty tricky because of lanthanoid contraction. Due to lanthanoid
contraction, they have almost identical sizes (Zr = 160 pm and Hf =159 pm) and, thus, similar
chemical properties. That’s why it is tough to separate them by chemical methods.
46.Although fluorine is more electronegative than oxygen, but the ability of
oxygen to stabilise higher oxidation states exceeds that of fluorine. Why?
Answer:Oxygen can form multiple bonds with metals, while fluorine can4t form multiple bonds.
Hence, oxygen has more ability to stabilise a higher oxidation state rather than fluorine.
47.Although Cr3+ and Co2+ ions have same number of unpaired electrons, but the
magnetic moment of Cr3+ is 3.87 B.M. and that of Co2+ is 4.87 B.M. Why?
Answer:Due to symmetrical electronic configuration, there is no orbital contribution in the Cr 3+ ion.
However, appreciable orbital contribution takes place in Co2+ ions.
