D AND F BLOCK ELEMENTS

D Block Elements

1. What are transition elements ?

Ans :- The one which has incomplete d-orbital either in its ground state or in any of
its oxidation state is said to be a transition element.
2. What is the general electronic configuration of a transition element ?
Ans :- (n-1)d1-10 ns2
3. Why Zn, Cd, Hg are not regarded as transition elements ?
Ans :- Because they have completely filled d-orbital ( d10) in their ground state and in
their oxidation state.
4. On what ground can you say that ‘Sc’ is a transition element but not ‘Zn’ ?
Ans :- ‘Sc’ has incomplete d-orbital in its ground state but ‘Zn’ has completely filled
d-orbital in its ground state and in its +2 oxidation state.
5. ‘Ag’ atom has completely filled d-orbital in its ground state then how is it considered
as a transition element ?
Ans :-When ‘Ag’ exhibits +2 oxidation state, its electronic configuration in the
oxidation state is 4d9 (incomplete d-orbital), hence is considered as a transition
element.
6. Why do transition elements have high melting point ?
Ans :- Because of the involvement of greater no. of d & s-electrons for strong inter
atomic metallic bonding , melting point is high.
7. Explain the trend in M.P and B.P of transition elements?
Ans:- a) The M.P and B.P rises to the middle in every series because of increase in
the no. of unpaired electrons till the middle and then falls regularly because of the
decrease in unpaired electrons. Cr, Mo, W have high M.P in their respective series.
b) Zn, Cd and Hg have low M.P because of the absence of unpaired electrons.
8. Why do transition elements exhibits higher enthalpy of atomisation ?
Ans:- Because of the presence of unpaired electrons they undergo strong inter atomic
metallic bonding and hence exhibits higher ∆Hatm.
9. Comment on Enthalpy of Atomisation of transition elements?
Ans:-They have high enthalpies of atomization. Metals of 4d and 5d series have
∆Hatm greater than 3d series.
10.In the series from ‘Sc’ to ‘Zn’, ∆Hatm of Zn is lowest. Why ?
Ans:-Because of the presence of completely filled d-orbital in Zn, lesser is the
inter atomic metallic bonding hence less ∆Hatm.
11.Comment on Atomic and Ionic radii of transition elements?
Ans:- a)Ionic and Atomic radius decreases in a series in the beginning and then
remains almost constant in the middle and increases towards the end because of
increase in screening effect towards the end .
b) the radii of 5d series are virtually the same as those of the corresponding members
of the 4d series.
12.Why the radii of 5d series are virtually the same as those of the corresponding
members of the 4d series ?
Ans :- Because of Lanthanoid contraction.
13.What is Lanthanoid contraction ?
Ans :-A steady decrease in atomic and ionic radii due to the poor intervention of 4f
electrons.
14.Comment on Ionisation Enthalpy of transition elements?
a. ∆Hionization (Ionization Enthalpy) increases in each series of transition.
b. ∆H <∆H <∆H in every series of transition elements.
15.Why is ∆H higher for Cu and Cr ?
Ans :- After the removal of 1st electron the electronic configuration of Cu+ is 3d10
and Cr+ is 3d5 and the 2nd electron is to be removed from stable d-orbital. Hence 2nd
ionization enthalpy (∆H )for Cu and Cr is high.
16.Why ∆H is greater for Zn and Mn ?
Ans :- Because the 3rd electron has to be removed from stable d-orbital.
(Mn+2-3d5, Zn+2-3d10)
17.Note:- Electrode potential of an element is the measure of value of the change in the
following enthalpies ∆H ionization+∆Hatomisation+∆HHydration
Along with it the electronic configuration also decides the electrode potential.
18.The reduction potential value for Cu is +ve but that of Ni +2 is –ve. Justify ?
Ans :- For Cu, it is +ve because of high ∆Hatm but Ni it is –ve because of high
negative value of hydration enthalpy.
19.Why the E0Sc+3/Sc+2 and E0Fe+3/Fe+2 is low ?
Ans- Sc+3 has a stable noble gas configuration and hence has less affinity to get
reduced to Sc+2. Similarly Fe+3 has stable 3d5 configuration. Hence has less affinity to
change to Fe+2 which counts towards the low values of electrode potential.
20.Note:-
a. Larger is the electrode potential value of the redox couple, they act as stronger
oxidizing agents in aqueous solution and lesser is the electrode potential of the
redox couple, they act as stronger reducing agents.
b. Lower is the reduction potential value of a redox couple, more stable is its
higher oxdn state.
Lower is the reduction potential value of a redox couple, more stable is its
higher oxdn state and vice versa.
Ex – E0Sc+3/Sc+2is low which means Sc+3 is more stable than Sc+2 because Sc+3
has noble gas configuration.
E0Mn+3/Mn+2is high which means Mn+2 is more stable than Mn+3 because Mn+2
has d5 configuration.
21. Why Cr+2 is reducing agent and Mn+3 is oxidizing agent when both of them have d4
configuration?
Ans :- Cr+2 – 1electron  Cr+3(stable t23g configuration)
(3d4) (3d3) (stable configuration)
Mn+3+1electron Mn+2
(3d4) (3d5) (stable configuration)
22.Why is the E0 value for the Mn+3/Mn+2 couple much more positive than that for
Cr+3/Cr+2 or Fe+3/Fe+2? Explain.
Ans :-Because the 3rd ionization enthalpy of Mn is very high because of stable d5
configuration of Mn2+.
23.Which is a stronger reducing agent Cr+2 or Fe+2 is an aqueous medium and why ?
Ans :- Cr+2 is a stronger reducing agent than Fe+2.
Reason :- d4d3(t2g)occurs in case of Cr+2 but d6d5 occurs in case of Fe+2. Cr3+ ion
has d3 configuration (t2g3eg0), which makes Cr3+ stable in aqueous medium by providing
crystal field stabilization energy. Thus, Cr2+ ion can easily changes to Cr3+ (i.e. get
oxidised) and acts as a strong reducing agent.
24.For the first row transition metals the E0 Values are :-
E0 V Cr Mn Fe Co Ni Cu
+2
(M /M) -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34
Explain the irregularity in the above values.
Ans :- Because of irregular variation of ionisation enthalpies and also sublimation
enthalpies which are relatively much less for Manganese and Vanadium.
25.For M+2/M and M+3/M+2 systems the E0 values for some metals are as follows :-
Cr+2/Cr = -0.9v ; Cr+3/Cr+2 = -0.4v
Mn+2/Mn = -1.2v ; Mn+3/Mn+2 = +1.5v
Fe+2/Fe = -0.4v ; Fe+3/Fe+2 = +0.8v
Use this data to comment upon :-
a. The stability of Fe+3, Cr+3, Mn+3 in acid medium in comparison to each other.
b. The ease with which iron can be oxidized as compared to a similar process for
either chromium or Manganese metal.
Ans :-
a. Cr+3> Fe+3> Mn+3
b. Mn> Cr > Fe
(Note :- Lower is the reduction potential value more stable is its higher
oxidation state.)
26.Note:-
a. An ion is stable in aqueous medium because of high –ve hydration enthalpy.
b. Higher is the oxidizing state of a metal, higher is its oxidizing power.
27.Why Cu+2 ion in aq. State is more stable than Cu+1inspite of d10 configuration?
Ans :- Cu+2 ion is associated with –ve high hydration enthalpy.
28.How would you account for the inc.oxidising power in the series ?
VO2+< Cr2O72-< MnO4-
Ans :-Mn has higher oxidation state (+7) hence higher is the oxdising power.
29.Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only ?
Ans :- Because Oxygen and fluorine are highly electronegative in nature and a metal
in its highest oxidation state is electropositive in nature .
30.Why transition elements have variable oxidation state ?
Ans :- Due to availability of unpaired d-electrons, transition elements have variable
oxidation state(ex- Sc and Zn)
Sc+3; Ti  +2; V +3,+4,+2,+5; Cr+2….+6; Mn+2….+7
Fe+2,+3,+4 and +6 unstable; Co+2,+3+4;Cu +1,+2; Zn+2.
31.Note:-
a. Higher is the oxidation state, more is the stability.
b. At lower oxidation state elements go for ionic bonding and at higher oxidation
state elements go for covalent bonding. Oxides of transition elements with
higher oxidation state of the metal is covalent or acidic in nature.
Example-MnO is basic and Mn2O7 is acidic and covalent in nature.
32.Name a transition element which does not exhibit variable oxidation state ?
Ans :- Scandium
33.Which of the 3d series of the transition metals exhibits largest no. of oxidation state
and why ?
Ans :-Mn because of participation of both ns and (n-1)d electrons.
34.Why are the transition metals paramagnetic ?
Ans :- Because of the presence of unpaired electron.
35.Note:-Magnetic moment = 𝑛(𝑛 + 2) ; Unit – Bohr Magneton.
36.Why do transition metals form coloured ions ?
Ans :- Because of t2g-eg transition.
37.Why do they form complex compounds ?
Ans :- Because of small size, availability of vacant d-orbitals and high ionic charges.
38.Why do they act as catalyst ?
Ans :-Their ability to adopt multiple oxidation state and to form complexes.
39.What do you mean by diproportionation reaction ?
Ans :-When in a reaction a particular oxidation state moves to a higher oxdn state and
simultaneously lower oxidation state, they are said to undergo disproportionation
reaction.
3MnO42-+4H+2MnO4-+MnO2+2H2O.
40.Note:-Smaller the ∆ Hionisation of a metal greater is its thermodynamic stability.
Forex – Ni+2 is more thermodynamically stable than Pt+2 because
(∆H1i+∆H2i) of Ni< (∆H1i+∆H2i) of Pt. Similarily Pt+4 is more thermodynamically
stable than Ni+4.
41.How would you account for irregular variation in ∆Hionisation in the 1st series of the
transition elements ?
Ans :- Because of irregularity in atomic size and also electronic configuration.
42.Give reasons :-
a. Cu+ is colourless whereas Cu+2 in aqueous solution is blue.
 b. Transition metal ions like Cu+ and Ag+ are colourless.
c. Chromium group elements have the highest melting points in their respective
series.
Ans :-a)Cu+2 has 1 unpaired 𝑒 hence undergoes d-d transition and is coloured.
b)Because of absence of unpaired 𝑒 s.
c)Due to presence of maximum no. of unpaired 𝑒 s.
43.Out of the Ag+, Co+2, Ti+4, Cr+2 if each one of the above ionic species is in turn placed
in a magnetic field, how will it respond and why ?
Ans :- Co+2 and Cr+2 will be attracted by magnetic field because of the presence of
unpaired 𝑒 s.
44.A blackish brown coloured compound ‘A’ when fused with alkali metal hydroxides
in presence of air, produces a dark green coloured compound ‘B’ which on
electrolytic oxidation in alkaline medium gives a dark purple coloured compound
‘C’. Identify A,B,C and write the reaction of A when fused with alkali metal
hydroxide in presence of air. What happens when an acidic solution of green
compound ‘B’ is allowed to stand for sometime. Give the equation involved ? What
is this type of reaction called ?
Ans :- A = MnO2; B = K2MnO4; C= KMnO4
2MnO2+2KOH+O22K2MnO4+2H2O
3K2MnO42KMnO4+MnO2+2H2O
Disproportionation Reaction.
45.A mixed oxide of iron and chromium FeO.Cr2O3 is fused with Na2CO3 in the
presence of air to form a yellow coloured compound ‘A’. ;On acidification the
compound ‘A’ forms an orange coloured compound ‘B’, Which is a strong oxidizing
agent. Identify :-
a. The compound A and B
b. Write balanced chemical equation for each step.
Ans :- A = Na2CrO4, B =Na2Cr2O7
4FeCr2O4+8Na2CO3+7O28Na2CrO4+2Fe2O3+8CO2.
46.When a brown compound of manganese (A) is treated with HCI d gives a gas (B).
The gas taken in excess reacts with NH3 to give an explosive compound (C). Identify
compounds A and B.
Ans :- A = MnO2 B = Cl2 C=NCl3
MnO2+4HCIMnCl2+Cl2+2H2O
 (A) (B)
NH3+3CI2NCI3+3HCI.
(excess) (C)
47.A green solution of potassium manganate turns purple when CO2 gas is passed
through the solution. Explain why ?
Ans :- CO2+H2OH2CO3⇄H++HCO3-
3MnO42-+4H+2MnO4- + MnO2+2H2O(Acidic Medium)
Green Purple
48.When an oxide of manganese (A) is fused with KOH in the presence of an oxidizing
agent and dissolved in water, it gives a dark solution of compound (B). Compound
(B) disproportionates on neutral or acidic solution to give purple compound (C). An
alkaline solution of compound (C) oxidizes potassium iodide solution to a compound
(D) and compound (A) is also formed. Identify compounds A to D and also explain
the reactions involved.
Ans :- A = MnO2 B = K2MnO4 C=KMnO4 D = KIO3
2MnO2+4KOH+O22K2MnO4+ 2H2O
3MnO42- + 4H+  2MnO4- + MnO2+ 2H2O
2MnO4- +H2O + KI2MnO2+2OH- + KIO3

49.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.
Ans :- A = KMnO4, B = K2MnO4, C = MnO2, D = MnCl2
∆
2KMnO4→K2MnO4+MnO2+O2
2MnO2+4KOH+O22K2MnO4+2H2O
MnO2+4NaCl+4H2SO4MnCl2+4NaHSO4+2H2O+Cl2
F- Block Elements

1. Note:- General Characteristics of Lanthanoids :-

a. It involves filling up of 4f-orbitals.
b. The general electronic configuration is (n-2)f1-14(n-1)d0-1ns2.
c. It starts from Cerium (Ce) and ends at Lutetium (Lu).
d. They exhibit +2 and +4 oxidation state. (+2 is the common oxidation state)
e. Stable electronic configuration are f0, f7, f14.
f. Most of the Lanthanoids, especially trivalent ions are coloured due to f-f
transition.
g. They are paramagnetic in nature due to presence of unpaired electrons in f-
orbitals.
h. They are highly electropositive and reactive.
i. Their nitrates, chlorides, acetates are soluble in water.
j. There is a steady decrease in their atomic size with increase in atomic number
called Lanthanoid contraction. It is due to increase in effective nuclear charge
and poor intervention of 4f electrons.
2. What are the consequences of Lanthanoid contraction ?
Ans :-
a. The elements of 2nd and 3rd transition series resemble each other much more
than the elements of 2nd and 1st transition series.
b. It is very difficult to separate the elements in pure state because their chemical
properties are quite similar.
c. The basic strength of hydroxides of Lanthanoids decreases with increase in
atomic number.
d. Zr and Hf have identical sizes.
3. Note:- General characteristics of Actinoids :-
a. They include 14 elements having at no. 89 to 103. All of them are radioactive
in nature.
b. The most common oxidation state is +3 but they also show +2, +4, +5 and +6.
c. They are paramagenetic in nature due to presence of unpaired electrons.
d. They form coloured ions.
e. They form oxo-cations in higher oxidation state.
f. They are highly electropositive and forms salts as well as complexes.
g. They are basic in nature .
4. What is Actinoid contraction ?
Ans :- The atomic and ionic size decreases with increase in atomic number electrons
are added to f orbitals. As a result the nuclear charge increases due to poor
intervention of 5f electrons. This results in shrinkage of atomic size.
5. Why is Actinoid Contraction greater than Lanthanoid Contraction?
Ans:-Actinoid Contraction is more in comparison to Lanthanoid Contraction because
5f electrons provide poorer intervention than 4f electrons.

Difference between Lanthanoids and Actinoids ?

Lanthanoids Actinoids
a) 4f orbitals are filled. a) 5f orbitals are filled.
n
b) +3 oxd . State most common b) They exhibit +2 to +7oxdn
along with +2 and +4. states.
c) Only promethium is c) All are radioactive in nature.
radioactive.
d) Lanthanoids are less reactive. d) Actinoids are more reactive.
e) Less complex magnetic e) The magnetic nature cannot
properties or can be easily be explained easily. The
explained. observed values do not tally
with the expected values.
f) Most of the tripositiveions are g) Most of the tripositive and
colourless. tetrapositive ions are
coloured.
h) They have less tendency to h) Have a stronger tendency
form complex. towards complex formation.
6. Name a member of lanthanoid series which is well known to exhibit +4 oxidation
state.
Ans :- Cerium.
7. Lanthanum, Gadolinium, Lutetium are extra ordinarily stable in their +3 oxidation
state. Explain
La+3f0; Gd+3; Lu+3f14 configuration which makes them stable.
8. Give reasons :-
a. Size of trivalent cations decrease with the increase in atomic no.
b. Among, the Lanthanides, Ce(III) is easily oxidized to Ce(IV).
c. Actinoids exhibit a greater no. of oxdn state than Lanthanoids.
d. Separation of Lanthanoid elements are difficult.
 e. Actinoid contraction is greater from element to element than Lanthanoid
contraction.
f. Europium (II) is more stable than Cerium (II).
g. Actinoid ions are generally coloured.
h. Among lanthanoids, Ln(III) compounds are predominant. However
occasionally in solutions or in said compounds +2 and +4 ions are also
obtained.
Ans :-
i. Due to Lanthanoid contraction.
ii. Ce+3-1e Ce+4
(fI) (f0) more stable configuration.
iii. Due to small energy gap between 5f, 6d, and 75 subshell of actinoids.
iv. Due to poor shielding effect of 5f electrons of actinoids than 4f electrons
of Lanthanoids.
v. Eu+2f7configuration hence more stable.
vi. Unpaired electrons present undergo f-f transition.
vii. Lanthanoid metals show +2 and +4 oxidation state to attain extra stable
f0 and f7 configuration.
9. Why Lu(OH)3 is a weaker base than La(OH)3 ?
Ans :- In the Lanthanide series the ionic size decreases from La +3 to Lu+3 hence
covalent nature increases thereby decreasing the basic strength.
10.On the basis of lanthanoid contraction, explain the following :-
a. Nature of bonding in La2O3 and Lu2O3.
b. Trends in the stability of oxo salts of lanthanoids from La to Lu.
c. Stability of the complexes of Lanthanoids.
d. Radii of 4d and 5d block elements.
e. Trends in acidic character of lanthanoid oxides.
Ans :-
a. As the size decreases covalent character increases. Therefore La2O3 is more
ionic and Lu2O3 is more covalent.
b. As the size decreases from La to Lu, stability of oxo salts also decreases.
c. They give stable complexes.
d. Radii of 4d and 5d block elements will be almost same.
e. Acidic character of oxides increases from La to Lu.
 11.Why is the chemistry of Actinoids is more complicated than Lanthanoids?

Ans:-Because they show a wide range of oxidation state and are radioactive in nature.

Note:-POINTS OF RESEMEBLANCE BETWEEN ACTIONOIDS AND

LANTHANOIDS

i. Both lanthanoids and actinoids show a dominant oxidation state of +3.

ii. Both are electropositive and act as strong reducing agents.3
iii. Cations with unpaired e𝜃s in both of them are paramagnetic.
iv. Most of the cations of lanthanoids and actinoids are coloured.
v. Both of them show a steady decrease in their ionic redii along the series.