CHAPTER – 8

d-AND f-BLOCK ELEMENTS

Q.1# Why Zn ,Cd, and Hg are Ans—They do not have unpaired d-electrons in the ground state as
normally not considered as Transition well as in their common oxidation states.
metals. **The electronic configurations of Zn, Cd and Hg are represented by
the general formula (n-1)d10ns2. The orbitals in these elements are
completely filled in the ground state as well as in their common
oxidation states. Therefore, they are not regarded as transition
elements.
Q.2# Transition elements show Ans--due to very little energy difference of energy between (n-1)d
variable oxidation states.Write all the and ns orbitals.
possible O.S. of an element (Z=25) The tendency to take part ‘(n-1)d’ as well as outermost ‘ns’-
electrons in bond formation –**When ns electron participate in
bonding—Low O.S and when (n-1)d and ns take part in
bonding—Higher OS results
Q.3# Transition metals have high Ans-- Because of large number of unpaired d-electrons in their
boiling points and have high atoms they have stronger inter-atomic interaction and hence
enthalpies of atomization . (AI-05) stronger bonding between atoms resulting in higher enthalpies of
atomisation.
(both metallic and d-d- overlapping of covalent bond )
**One unpaired electron per d orbital is particularly favourable for
strong interatomic interaction
Q.4# Transition metals and many of Ans—Due to spin and orbital motion of negatively charged
their compounds show paramagnetic unpaired d-electron(s) in an atom ,ion or molecule
behaviour . (AI-05)
Q.5# Transition metals generally from Ans--Due to d-d transition of unpaired d-electron .
color compound (AI-08) The unpaired electron excited from lower energy d-orbital to higher
energy d-orbital(CFT), the energy is absorbed from visible region of
radiation and the complementary part of absorbed light( i.e.
reflected light) will decide the colour of the compound
Q.6# Transition metals and many of Ans-- catalytic activity is ascribed to their
their compound act as a good catalyst 1) ability to adopt multiple oxidation states and
. (AI-05) 2) to form complexes. (form different intermediate with any
oxidation states which may lead through lower activation energy
path).
** In some cases , the T.Metals provide s suitable large surface area
with free valencies on which reactants are adsorbed .
**(Due to their tendency to show variable oxidation states TM
forms unstable intermediate compounds and provide a new path for
the reaction with lower activation energy path)
Q.7# Transtion metals form complex Ans--This is due to the high (charge / radius) ratio and empty d-
compounds. orbital .
1) comparatively smaller sizes of the metal ions,
2) their high ionic charges and
3) the availability of empty d orbitals for bond formation.
Q.8 # Transition metal generally form Ans— Because of similar radii and other characteristics of transition
alloys with other transition metals. metals, alloys are readily formed by these metals. Alloys are formed
by atoms with metallic radii that are within about 15 percent of each
 other. Substitutional and interstitial alloy .
Q.9 # Transition metals form a Ans-- It because transition metals have voids in their crystal lattice ,
number of interstitial compounds in which small atoms of H , C , N can fit forming interstitial
compounds which do not have fixed composition . The trapped
atoms get bonded to the atoms of TE . e.g. TiC , Fe3H , Mn4N
Q. 10 # There is hardly any increase in ANS- This is because with increase in atomic number in a series , the
atomic size with increasing at.no. in a increases nuclear charge is partly cancelled by the increased
series of transition metals . shielding effect of electrons in the d-orbitals of penultimate shell .
Q.11# What is lanthanide contraction Ans-- The overall decrease in atomic and ionic radii from lanthanum
? State the cause and two to lutetium
consequences of lanthanide Cause- due to the imperfect shielding of one f-electron by another in
contraction . the same sub-shell. and the dominance of nuclear charge .
The extra orbital electrons incompletely shielded the extra nuclear
charge.
Thus effective nuclear charge increases.Thus all the electrons are
pulled in closer
Consequences—(1) Thus pairs of elements such as Zr/Hf
(2)The first IE of 5d elements lie higher than those of 3d and 4d
elements
(3) The metallic radii of 5d and 4d are nearly same .
(4) it is difficult to separate lanthanoid elements
(5) La(OH)3 is more basic than Lu(OH)3
Q.12 # (a)Actinoid contraction is Ans—(a) The 5f electrons themselves provide poor shielding from
greater from element to element than element to element in the series as compared to 4f –electrons .
lanthanoid contraction. Why? As because 5f orbitals are comparatively larger and more diffused .
(b)There is a greater range of Imperfect screening is greater in case of 5f than in case of 4f .
oxidation states among the Actinoids Ans—(b) Due to the fact that 5f, 6d and 7s levels are of comparable
than that in Lanthanoids energiesi.e the energy differences are very less , so electron can
participate from all three sub-shells .
Q.13 # WhyZr and Hf show similar Ans—It is due to similar ionic size which is due to lanthanoid
properties? contraction . (Due to the imperfect shielding of one f-electron by
another in the same sub-shell.)
Q.14# The 4d- and 5d-series of Ans – Due to lanthanoid contraction
transition metals have more frequent Due to the imperfect shielding of one f-electron by another in the
Metal-Metal bonding in their same sub-shell. and the dominance of nuclear charge .
compounds than do the 3d-metals . The extra orbital electrons incompletely shielded the extra nuclear
[(OR ,There occurs much more charge.
frequent metal-metal bonding in Thus effective nuclear charge increases.Thus all the electrons are
compounds of heavy transition pulled in closer
elements (3rd series).]
OR , The metallic radii of 5d and 4d
series are nearly the same .
OR ,There is a close similarity in
physical and chemical properties of
the 4 d and 5 d series of the
transition elements, much more than
expected on the basis of usual family
relationship.
Q.15 # The E0(M2+/M) value for copper Ans— The reduction potential value depends on relative value of
is positive (+0.34V). three enthalpies viz ΔaH0 , ΔiH0 and - ΔhydH0 . The copper has high ΔaH0
What is possibly the reason for this? and ΔiH0. Therefore high enthalpy required to transform Cu(s) to
Copper is the only metal in the first Cu2+(aq) is not balanced by its low ΔhydH0 .
series of Transition elements showing
this behavior ?
Q.16 # Why is Cr2+ strongly reducing Ans:- Cr2+ is reducing as its configuration changes from d4 to d3 (t2g3 ),
and Mn3+ strongly oxidising when both Cr3+ (t2g3 )-- As the having a half-filled t2g level .It has higher CFSE
have d4 configuration. than Mn2+ ( t2g3 eg2)
On the other hand, the change from Mn3+( d4) to Mn2+ (d5) results in
the half-filled (d5) configuration which has extra stability.
***In aqueous solution Cr3+(t2g3) has more stability than Mn2+ ( t2g3
eg2)
Q.17 # Explain why Cu+ ion is not Ans--Cu+ in aqueous solution underoes disproportionation,
stable in aqueous solutions? i.e., 2Cu+(aq) → Cu2+(aq) + Cu(s) . Cu ++ is more stable .
The E0 value for this is favourable. Cu++ has relatively higher
hydration enthalpy than Cu+
Q.18 # What is meant by When a particular oxidation state of an element becomes less
‘disproportionation’ of an oxidation stable relative to other oxidation state, one lower and one higher,
state? Give an example it is said to undergo disproportionation. For example, in aqueous
solution:
For example, (i) manganese (VI) becomes unstable relative to
manganese(VII) and manganese (IV) in acidic solution.
(i) 3 MnO42- + 4H+ ——> 2MnO42- + MnO2 + 2H2O
(ii) Cu+ disproportionate into Cu2+and Cu : 2Cu2+ Cu2+ +Cu
(iii) Mn3+ Mn2+ + MnO2
How would you account for the following: Ans— Co(III) has greater tendency to form coordination
Q.19# Cobalt(II) is stable in aqueous complexes than Co(II) .
solution but in the presence of complexing Due to higher charge by radius ratio and also due to greater CFSE
reagents it is easily oxidised. ( Crystal Field Stabilisation Energy) .Co (III) has d6 configuration
OR ,Co (II) is easily oxidised in the In case of of strong ligand , It is t2g 6 eg0 (stable configuration)
presence of strong ligands. So , Co(II) changes to Co(III) i.e. easily oxidized .
Q.20# Thed configuration is very
1 Ans-- The ions with d1 configuration have the tendency to lose the
unstable in ions. only electron present in d-subshell to acquire stable d0 configuration
(Argon configuration). Hence they are unstable and undergo
oxidation and disproportionation .
Q.21 # Mn compounds are more
+2 Ans-- Mn 3+ + e- ——>Mn 2+
stable than Fe+2 toward oxidation to (d4 system , less stable ) (d5 system , more stable )
their + 3 state .(AI-06) extra stable due to half-filled confN
OR , Why E0 for Mn+3 / Mn+2 couple is Fe3+ + e-  Fe 2+
more positive than for Fe+3 / Fe+2 or (d5system , more stable )(d6 system , less stable )
Cr / Cr .
+3 +2 Cr3+ + e- ——> Cr 2+
(t2g3 - half filled- more stable )(d4 system , less stable)
Much larger third Ionisation enthalpy of Mn( where the required
change is d5 to d4) is mainly responsible for this . this also explains
why the +3 state of Mn is of little importance
Cr3+ (d3), t2g 3 - half filled ) Higher Crystal Field stabilization energy .
(CFSE)
Q.22 # (a) There is no regular trend in Ans— The E0(M2+/M) values are not regular which can be explained
E 0 values in the series Vanadium from the irregular variationof ionization energies (IE1 + IE2) and also
( At No –23) to Copper(At No 29) for the sublimation energy which are relatively much less for Mn and
M /M system..
2+ Vanadium. (240kj/mol for Mn and 470 KJ/mol for Vanadium)
(ii) EoM2+ /M values are not regular for
first row transition metals (3d series).
Q.23 # How would you account for Ans--This is due to the increasing stability of the lower species to which
the increasing oxidising power in they are reduced.
the series VO < Cr2O7 < MnO ?
2+ 2– 4–

Q.24 # How would you account Ans-- Irregular variation of ionisation enthalpies is mainly attributed to
for the irregular variation of varying degree of stability of different 3d-configurations (e.g., d0, d5, d10
ionization enthalpies (first and are exceptionally stable).
second) in the first series of the
transition elements?
Q.25 # Why is the highest oxidation Ans-- Because of small size and high electronegativity oxygen or
state of a metal exhibited in its oxide fluorine can oxidise the metal to its highest oxidationstate.
or fluoride only? **The ability of fluorine to stabilise the highest oxidation state is
OR , due to either higher lattice energy as in the case of CoF3, or higher
Although ‘F’ is more electronegative bond enthalpy terms for the higher covalent compounds, e.g., VF5
than ‘O’, the highest Mn fluoride is and CrF6.
MnF4, whereas the highest oxide is The ability of oxygen to stabilise these high oxidation states exceeds
Mn2O7.—Explain that of fluorine. The ability of oxygen to form multiple bonds with
OR transition metal explains its superiority.
Why the highest oxidation state is Thus the highest Mn fluoride is MnF4 whereas the highest oxide is
exhibited in oxo-anions of a transition Mn2O7.
metal.? In the covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by
O’s including a Mn–O–Mn bridge.
Q.26# Which is a stronger reducing Ans-- Cr2+ is stronger reducing agent than Fe2+
agent Cr2+ or Fe2+ and why ? Reason:d4 → d3 occurs in case of Cr2+ to Cr3+ ((t2g3 - half filled- more
stable )
But d6 → d5 occurs in case of Fe2+ to Fe3+ .
In a medium (like water) d3is more stable (higher CFSE) as compared
to d5 .
Q.27 # Why is the E0 value for Ans--Much larger third ionisation energy of Mn (where the required change
the Mn /Mn couple much
3+ 2+ is d5 to d4) is mainly responsible for this. This also explains why the +3 state
more positive than that for of Mn is of little importance.
Cr /Cr or Fe /Fe ? Explain.
3+ 2+ 3+ 2+

Q. 28 # Among lanthanoids , Ln(III) compounds ANS- lanthanoid metals show +2 and +4 O.S to attain extra
are predominant . However , occasionally in stability of f0 f7 and f14 configuration .
solutions or in solid compounds , +2 & +4 ions Eu2+ ,Tb4+ -(4f7)-half filled . Ce4+ ( 4f0)
are also obtained .
Q.29 # How is the variability in ANS- In transition elements the oxidation states vary by one
oxidation states of transition metals For example, for Mn it may vary as +2, +3, +4, +5, +6, +7.
different from that of the non In the nontransition elements the variation is selective, always
transition metals? Illustrate with differing by 2, e.g. +2, +4, or +3, +5 or +4, +6 etc.
examples.
Q. 30 # Why there is general increase ANS- The decrease in metallic radius coupled with increase in atomic
in density from Ti to Cu . mass results in a general increase in density .
Q. 31 # The higher O.S are ANS- Due to presence of maximum number of unpaired electrons in a
usually exhibited by the members TM which is present in the middle of the series .
in the middle of the series of
Transition Elements.
Q. 32 # Mn2+ is much more resistant ANS-Mn2+(d5 , half-filled ) is stabler than Mn3+(d4) , so Mn2+ not easily
than Fe2+ towards oxidation . get oxidized
Fe2+(d6) is less stable than Fe3+ (d5 , half-filled) . so Fe2+ is easily get
oxidized to get stable configuration .
Q.38 #.Why is HCl not used to acidify a Ans-Since Cl¯ of Hydrochloric acid is oxidized to chlorine by MnO4¯ .
permanganate solutions in volumetric so , actual amount of KMnO4 required to oxidize C2O42‾couldnot be
estimation of Fe+2 or C2O42‾ . determined

Q.33 # Give reason for it?. Ni+2 compounds are Ans--The oxidation state of Pt in K2 Pt Cl6is +4 .The
thermodynamically more stable than Pt compounds
+2 sum of the first four ionization energies (IE1+IE2 +IE
whilstPt(IV) are relatively more stable than Ni(IV) 3+IE 4) of pt is less than those of Ni.

compounds . OR, K2PtCl6 is well known cpds. but

corresponding Ni-compound is not known .
Q.34 # E0 for Mn+3 / Mn+2 couple is Ans-- Much larger third Ionisation enthalpy of Mn ( where the
more positive than for Fe / Fe or
+3 +2 required change is d5 to d4) is mainly responsible for this . this also
Cr+3 / Cr+2 . explains why the +3 state of Mn is of little importance .

Q.35 # Why do transition elements Ans-- the high enthalpy of hydration of transition elements is due
have high enthalpy of hydration? to
(i) small size of the cation and
(ii) large positive charge e.g. Cu++ has higher enthalpy of
hydration than Cu+
Q.36 # For the first row transition metals the Eo values are: Ans--The E0 (M2+/M) values are not regular
E V
o Cr Mn Fe Co Ni Cu which can be explained from the irregular
M /M) -1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 +0.34 variation of ionisation enthalpies ( Δi H1+Δ iH2)
2+

-------- Explain the irregularity in the above values. and also the sublimation enthalpies which
are relatively much less for Mn and V..

Q. 37 # What are alloys? Name an Ans- Alloys may be homogeneous solid solutions in which the atoms
important alloy which contains some of one metal are distributed randomly among the atoms of the other
of the lanthanoid metals. Mention its
uses. A well known alloy is mischmetallwhich consists of a lanthanoid
OR , Write two uses of mischmetall metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al.
A good deal of mischmetall is used in Mg-based alloy to produce
bullets, shell and lighter flint.
Q.38 # What is the effect of increasing Ans- It will change to yellow colour by forming Potassium chromate
pH on a solution of K2Cr2O7 ( in alkaline medium)
K2Cr2O7 ( orange) ------ ( OH-)K2CrO4 ( Yellow)
** K2CrO4 ( Yellow) ------ ( H+)-K2Cr2O7 ( orange)
Q.39# W h a t chemical changes takes places w Ans (i) Potassium manganate (K2MnO4 –green ,
hen– paramagnetic)
(i) Pyrolusite is fused with KOH in the presence (ii) Pottasium Chromate (K2CrO4 – Yellow , diamagnetic)
of air (iii) K2Cr2O7 – Orange )
(ii) Chromite ore is fused with molten NaOH in (iv) (iv) Soluble complex , [Ag(NH3)2]Cl
presence of air (v) (v) Iodate (IO3¯ ) and Mn2+
(iii)When a solution of chromate is acidified
(iv)NH3 is added to a suspension of AgCl
(v) Alkaline KMnO4 reacts with KI
Q.40# Which is the last element in the Ans :-Lawrencium(103)
series of the actinoids? Write the 5f 146d17s2
electronic configuration of this +3
element. Comment on the possible
oxidation state of this element.
Q.41 # On what ground can you say Ans--On the basis of incompletely filled 3d orbitals in case of
that scandium (Z = 21) is a transition scandium atom in its ground state (3d1), it is regarded as a transition
element but zinc (Z = 30) is not? element. On the other hand, zinc atom has completely filled d
orbitals (3d10) in its ground state as well as in its oxidisedstate, hence
it is not regarded as a transition element.
Q.42# Silver atom has completely Ans--Silver (Z = 47) can exhibit +1 oxidation state wherein it will have
filled d orbitals (4d10) in its ground incompletely filled d-orbitals (4d), hence a transition element.
state. How can you say that it is a
transition element?
Q.43 # In the series Sc (Z = 21) to Zn (Z Ans- In the formation of metallic bonds, no eletrons from 3d-orbitals
= 30), the enthalpy of atomization of are involved in case of zinc, while in all other metals of the 3d series,
zinc is the lowest, i.e., 126 kJ mol–1. electrons from the d-orbitals are always involved in the formation of
Why? metallic bonds.
Q.44 # Name a transition element Ans--Scandium (Z = 21) does not exhibit variable oxidation states.
which does not exhibit variable Only oxidation states i.e Sc3+
oxidation states.
45# Name the element showing maximum Ans :Manganese (Z = 25), as its atom has the maximum
number of oxidation states among the first number of unpaired electrons. i.e five ( +2 , +3 , +4 , +5 , +6
series of transition metals from Sc (Z = 21) to , +7)
Zn (Z = 30).
OR , Which of the 3-d series of the transition
metals exhibits the largest number oxidation
states and why?
Q.46 # Calculate the magnetic Ans-- With atomic number 25, the divalent ion in aqueous solution
moment of a divalent ion in aqueous will have d5 configuration (five unpaired electrons). The magnetic
solution if its atomic number is 25. moment, μ is μ = √5(5+2) = 5.92BM
Q.47 # Calculate the ‘spin only’ Ans—three unpaired electron .μ = √3(3+2) = 3.87 BM
magnetic moment of M2+ (aq) ion (Z =
27).
Q.48 # Name a member of the Ans—(a) Cerium (Z = 58) Ce4+ : Xe] 4f0 accounts for its formation
lanthanoid series which is well known .
to (b) Eu . Eu2+ is formed by losing the two s- electrons and its Xe]
(a) exhibit +4 oxidation state. (AI14) 4f7 accounts for its formation .
(b) exhibit +2 oxidation state. (D-14)
Q.49 # Among the species Sc3+,.Ce4+, Ans--In all the above ion the most stable oxidising state is +3
and Eu which one is good oxidising
2+ .therefore Sc3+ will remain unchanged. Ce4+has the tendency to
agent ? accept one electron to get the +3 oxidation state. Hence Ce4+ is a
Sc ——>[A r] 3d 4s
3+ 0 0 good oxidising agent.Eu2+ has the tendency to lose one electron to
Ce4+ ——> [Xe] 4f0 5d0 6s0 get the +3 oxidation state. Hence Eu2+ is a good reducing agent.
Eu2+ ——>[Xe] 4f75d0 6s0
Q.50 # Mn (III) undergoes Ans : Mn (III) unstable oxidation states , it undergoes
disproportionation reaction easily. disproportionation to Mn2+ and MnO2 ( +4 oxidation states )
51 # Out of Mn3+ and Cr3+ , which is Ans :- Mn3+ (3d4 4s0 , four unpaired d- electrons ) -- more
more paramagnetic and why ? paramagnetic - higher no. of unpaired d- electrons Cr3+( 3d3 4s0 ,
three unpaired electron)
52# Which transition metal of 3d Ans :- Cu . The sum of high enthalpy of atomization and ionization
series has positive E (M /M) value
0 2+ enthalpy to transform Cu(s) Cu2+(aq) is not balanced by hydration
and why enthalpy .

53 # Sc3+ is colourless in aqueous Ans :-Sc3+ have no unpaired d- electron . No d—d transition of
solution whereas Ti3+ is coloured unpaired d-electron . BUT Ti3+ have one unpaired d- electron .d—d
(2014-F) transition of unpaired d-electron in visible region . The
complementary colour is seen .
54# La3+ (Z = 57) and Lu3+ (Z = 71) do Ans: La3+ : (Xe] 4f0 and Lu3+ (Xe] 4f14 - absence of unpaired f-
not show any colour in solutions. electrons for f—f transition . so no f—f transition in the visible
region .
55# Compare actinoids and lanthanoids with (i) In Lanthanoids electrons are filled in antepenultimate
special reference to their : shell i.e 4f subshell BUT in Actinoids 5f subshell
(i) electronic configurations of atoms (ii) +3 , +2 and +4 ( do not show greater range of O .S )
(ii) oxidation states of elements BUT in Actinoids +3 , +4 , +5, +6 &7
(iii) general chemical reactivity of elements. (iiI) Lanthanoids are less reactive whereas Actinoids( low
(iv) atomic and ionic sizes I.E) are more reactive chemically
(iv) Lanthanoids are smaller than the actinoids .
Q.56 # Calculate the number of unpaired Mn = 5 , Cr3+ = 3 , V3+ = 2 , Fe2+ = 4
2+

electrons in the following gaseous state Cr3+ , due to half-filled configuration

ions: Mn2+, Cr3+, V3+ and Fe2+ ( t2g3 eg0 ----- Higher crystal field stabilization energy .
Which one of these is the most stable
in aqueous solutions? (At. nos. V = 23, Cr
= 24, Mn = 25, Fe = 26)
Q.57 # Which of the following cations Cations are coloured in aqueous solutions:- V3+ (d1- )1-unpaired
are coloured in aqueous solutions and electron, Mn2+(d5) - 5 unpaired electron ,Ti3+(d1) - 1 unpaired
why? electron, Fe3+(d5- 5 unpaired electron) and Co2+(d7) - 3 unpaired
Sc , V , Ti , Mn ,Ti , Cu , Fe and Co . electron. Due to d-d transition of unpaired d- electrons
3+ 3+ 4+ 2+ 3+ + 3+ 2+

Q.58# Which metal in the first transition Cu as Cu+

series (3d series) exhibits +1 oxidation
state most frequently and why?
Q.59# Generally there is an increase Atomic size decreases from Ti to Cu .
in density of elements from titanium REASON:-Along a period ( 3d – series) Relative increase in nuclear
(Z = 22) to copper (Z = 29) in the first charge is more dominant than relative increase in screening effect
series of transition elements. in d- subshell( imperfect screening)
Atomic mass increases but volume decreases that’s why density
increases from Ti to Cu .
Q.60# The higher oxidation states are Due to the presence of higher number of unpaired electrons.
usually exhibited by the members in (Mn shows O.S from +2 to +7)—present in the middle of the
the middle of a series of transition series .
elements.
Q.61# There is a greater horizontal Atomic sizes are very close by along the d- series
similarity in the properties of the
transition elements than of the main
group elements.
Q.62# The third ionization Due to half –filled configuration.( extra stable- ) Removing third
enthalpy of manganese (Z = 25) is electron from Mn2+ needs high I.E ( tightly held)
exceptionally high.
Q.63# Discuss the relative Mn-- 3d5 4s 2
stability in aqueous solutions of Due to half –filled configuration.( extra stable- )-- Mn2+ - -- 3d54s0
+2 oxidation state among the Cr--3d 5 4s 1 ; Cr2+--3d 4 4s 0 (unstable)
elements : Cr,Mn, Fe and Co. How Cr3+ , Stable-due to half-filled configuration – Stable O.S. In aq. Solution
would you justify this situation? ( t2g3 eg0 ----- Higher crystal field stabilization energy ) CFT
(At. Nos. Cr = 24, Mn = 25, Fe = Co--3d 7 4s 2 ; Co2+--3d 7 4s 0 (unstable)
26, Co = 27) Fe --3d 4s ; Fe - 3d 4s (unstable)
6 2 ++ 6 0

Q.64 # What may be the possible oxidation 3d 3 4s 2--- (+2 ,+3 ,+5- stable)
states of the transition metals with the 3d5 4s 2---( +2 , +3 , +4 , +5 , +6 , +7)
following d electronic configurations in the
ground state of their atoms: 3d 6 4s 2 –(+2, +3)
3d 3 4s 2 , 3d5 4s 2 and 3d 6 4s 2 . Indicate relative
stability of oxidation states in each case.
Q.65 # Among the divalent cations in the first Ans : Due to highest number of unpaired d- electron ( i.e
series of transition elements, manganese 5 ) [ 3d5 4s0 ]
exhibits the maximum paramagnetism.
Q.66 # Mn3+ is a good oxidising agent Mn (II) stable – d5 configuration . (-half filled configuration- stable)
. So Mn (III) being unstable get itself reduced to stable Mn(II) and
act as oxidizing agent .
Q.67 # Give reason (i) 57La—[Xe]54 4f 5d 6s
1 0 2 ;
57La —[Xe]54 4f 5d 6s -- fulfilled
3+ 0 0 0

(i) The +3 oxidation state of 57La , 64Gd configurtaion

, 71Lu are especially stable . 64Gd--- —[Xe]54 4f 5d 6s
7 1 2 ; Gd3+--- —[Xe]
64 54 4f75d06s0 -half –filled
(ii) Ce3+ can be easily oxidized to Ce4+ 71Lu----—[Xe]54 4f 5d 6s ; 71Lu ----—[Xe]54
14 1 2 3+ 4f145d06s0- fulfilled
configuration
(ii)Due to fulfilled configuration of Ce4+ - (Noble gas configuration-
Configuration of Xe) –stable . Ce3+ can be easily oxidized to Ce4+
Q.68# What are the characteristics of 1. High enthalpy of atomization. 2. Show paramagnetism 3.
the transition elements and why are Show colour compounds 4. Complex formation ability 5 . Show
they called transition elements? variable oxidation states .etc …( unique properties of
Transitional metals)
2. They show transitional characteristics between s- block and p-
block elements .
Q.69 # What are the different +3 ( commonOxidatyion States) +2 and +4 are also seen due to half
oxidation states exhibited by –filled and fulfilled configuration of various ions.
the lanthanoids?
Q. 70 # Which of the d-block Zn , Cd and Hg - Due to absence of Unpaired d- electrons either in the
elements may not be regarded ground state or in their commonly found Oxidation states .
as the transition elements?
Q.71 # Name the oxometal anions of the Permanganate ( MnO4 ¯ ) , +7-- Oxidation state , Mn belongs
first series of the transition metals in which to 7th group .
the metal exhibits the oxidation state equal
to its group number.
Q.72 # How is the variability in Oxidation states in Transition metals differs by one
oxidation states of transition metals BUT , in Non- transition metals O.S differs by 2
different from that of the non transition Phosphorous - +3 and +5 ( as in P2O3 and P2O5 )
metals? Illustrate with examples. Iron – Fe2+ and Fe3+
Q.73 # What are interstitial Ans-- It because transition metals have voids in their crystal lattice ,
compounds? Why are such in which small atoms of H , C , N can fit forming interstitial
compounds well known for transition compounds which do not have fixed composition . The trapped
metals? atoms get bonded to the atoms of TE .e.g. TiC , Fe3H , Mn4N ,VH0.56
TiH1.7 .
** Due to variable O.s of Transition metals , Metal deficient defects

are seen in solid state compound like FeO and NiO

Q.74 # To what extent do the electronic due to half –filled and fulfilled configuration of various ions.
configurations decide the stability of Mn-- 3d5 4s 2Mn2+ - -- 3d54s0(half –filled )
oxidation states in the first series of the Zn --3d10 4s 2, Zn++ --3d10 4s 0 (fulfilled configuration)
transition elements? Illustrate your
answer with examples.
Q.75 # Write down the Hydrated ions (octahedral)–water is the ligand ( weak field – high spin
number of complex ) Δ0< P
3d electrons in each of the Ti2+ ----(2 unpaired d- elctrons)3d24s0--- t2g2eg0
following ions: Ti2+, V2+, Cr3+, V2+--(3 unpaired d- elctrons)--3d34s0---- t2g3eg0
Mn2+, Fe2+, Fe3+, Co2+, Ni2+ andCr3+--(3 unpaired d- elctrons)-3d34s0------ t2g3eg0
Cu2+. Indicate how would you Mn2+-(5 unpaired d- elctrons)3d54s0-- t2g3eg2
expect the five 3d orbitals to Fe2+--(4 unpaired d- elctrons)-3d64s0- t2g4eg2
be occupied for these Fe3+--(5 unpaired d- elctrons)-3d54s0-- t2g3eg2
hydrated ions (octahedral). Co2+---(3 unpaired d- elctrons)-3d74s0-- t2g5eg2
Ni2+---(2 unpaired d- elctrons)-3d84s0-- t2g8eg2
Cu2+---(1 unpaired d- elctrons)3d94s0-- t2g6eg3
Q.76 # What can be inferred from the Magnetic moment depends on spin and orbital motion of negatively
magnetic moment values of the charged unpaired electron .by knowing magnetic value we can
following complex species ? predict the number of unpaired d- electron(s).
Example Magnetic Spin –only formula , µ = [n(n+2)]1/2 = [1(1+2)]1/2 = 1.73 BM
Moment (example)
(BM) Example Magnetic No.of configuration
K4[Mn(CN)6] 2.2 Moment( unpair
[Fe(H2O)6] 2+ 5.3 BM) ed
K2[MnCl4] 5.9 electro
n
K4[Mn(CN)6 2.2 1 t2g5eg0 (Strong Oh--CFT
] field)
[Fe(H2O)6]2+ 5.3 4 t2g4eg2 (weak
field)
K2[MnCl4] 5.9 5 eg2t2g3(weak field)

Atomic numbers 61--[Xe]544f 5 5d0 6s 2

Q.77 # Write the electronic Atomic numbers 91--[Rn]86 5f 26d17s 2
configurations of the elements with Atomic numbers 101-[Rn]86 5f 136d07s 2
the atomic numbers 61, 91, 101, and Atomic numbers 109 ---[Rn]86 5f 146d77s 2
109.
Q.78# What are inner transition Lanthanoids ( 4f – series from 6th period and 3rd group) and
elements? Decide which of the following actinoids( 5f – series from 7th period and 3rd group) are known as
At.nos are of the inner transition Inner transition elements :
elements :29, 59, 74, 95, 102, 104. Lanthanoids-- 59
Actinoids-- 95, 102

Q.79 # Sm2+ , Eu2+ and Yb+2 ** Sm+2(f 7) ,Eu+2(f 7),Yb+2(f 14) Sm+3,Eu+3, Yb+3 ( Stable , common O.S)
ions in solutions are good (Sm2+ , Eu2+ and Yb+2 ions tendency to change into +3 O.S.)-- [ Acts as reducing
reducing agents but an aq. agent)
Solution of Ce4+ is a good ** Tb+4(f 7) , Ce+4(f0) Tb+3 , Ce+3 ( Stable , common oxidation states)
oxidizing agent (tendency to change into +3 O.S.)-- [ Acts as oxidizing agent]

Q.80 # The outer electronic Xe is the noble gas core whose atomic number is 54
configurations of two members of the [Xe]544f1 5d 1 6s 2-- Atomic number is 58 ; stable O.S . +4 (empty
lanthnoid series are as follows : 4f 1 conf.)
5d 6s and 4f 5d 6s . What are
1 2 7 0 2 [Xe]544f7 5d 0 6s 2-- Atomic number is 63 ; stable O.S +2 (half-filled
their atomic numbers?Predict the conf.)
Oxidation States exhibited by these
elements in their compounds . (AI-
05)
Q.81 # Use Hund’s rule to derive the 58Ce—[Xe]54 4f 5d 6s
1 0 0 Only one unpaired electron is present
electronic configuration of Ce ion,
3+ Spin –only formula , µ = [n(n+2)]1/2 = [1(1+2)]1/2 = 1.73 BM
and calculate its magnetic moment on
the basis of ‘spin-only’ formula.

Preparation , properties and uses of

Potassium dichromate K2Cr2O7 and Potassium permanganate KMnO4
Describe the preparation of potassium dichromate Describe the preparation of Potassium
from iron chromite ore. permanganate KMnO4

Potassium dichromate K2Cr2O7 – Preparation , and Potassium permanganate KMnO4- Preparation , and
uses uses
STEP-1: Fusion of chromite ore (FeCr2O4) with
sodium potassium carbonate in free access of air ( Potassium permanganate is prepared by fusion of
Alkaline Oxidation) MnO2 with an alkali metal hydroxide and an
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 oxidising agent like KNO3. This produces the dark
CO2 green K2MnO4 which disproportionates in a neutral
STEP-2:The yellow solution of sodium chromate is or acidicsolution to give permanganate.
filtered and acidified with sulphuric acid to give a STEP-1 : 2MnO2 + 4KOH + O2 → 2K2MnO4 (dark
solution from which orange sodium dichromate, green)+ 2H2O
Na2Cr2O7. 2H2O can be crystallised. STEP-2 :3MnO42– + 4H+ → 2MnO4– (dark purple or
2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O almost black crystals)+ MnO2 + 2H2O
***Sodium dichromate is more soluble than Commercially it is prepared by the alkaline oxidative
potassium dichromate. fusion of MnO2 followed by the electrolytic oxidation
STEP-3:Potassium dichromate is therefore, prepared of manganate (Vl).
by treating the solution of sodium dichromate with STEP-1 : MnO2 ( fused with KOH, oxidized with air or
potassium chloride. KNO3)  MnO42– (manganate ion)
Na2Cr2O7 + 2 KCl → K2 Cr2O7 (Orange crystals STEP-2 :MnO42– (manganate ion) on Electrolytic
crystallise out.) + 2 NaCl oxidation in alkaline solution  MnO4– (
**The chromates and dichromates are permanganate ion)
interconvertible in aqueous solution depending KMnO4 is used as (1) a strong oxidant use in labs
upon pH of the solution. The oxidation state of and industry as volumetric reagent in alkaline and
chromium in chromate and dichromate is the same. acidic media
2 CrO42– + 2H+ → Cr2O72– + H2O (2) Disinfectant for well water
Cr2O7 + 2 OH → 2 CrO4
2– - 2- (3) as bleaching agent for wood ,cotton ,silk and
USES: K2Cr2O7 is used as (1) primary standard in other textiles.
volumetric analysis (2) good preparative Oxidant in
organic chemistry (3) In leather industry for tanning
purpose(4) preparation of many azo compounds
Question for you *****
Q.1# 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
Q.2# Describe the preparation of potassium permanganate. How does the acidified permanganate solution react
with (i) iron(II) ions (ii) SO2 and (iii) oxalic acid? Write the ionic equations for the reactions.
Redox Reaction :-
1# In Acid Solution--Reduction half cell :MnO4¯ (permanganate) +8H+ + 5e-  Mn+2(manganous) + 4 H2O
Cr2O72¯ (dichromate) + 14H+ + 6e- 2Cr+3 +7H2O
Oxidation half cell : I¯(Iodide) I2 (Iodine) , S 2¯ (Sulphide) S(Sulphur) ,
Sulphite(SO32¯) sulphate(SO42¯) , Nitrite (NO2¯ ) Nitrate (NO3¯ )
Fe (Ferrous)  Fe+3 (Ferric) ,
+2 C2O42 ¯(oxalate)  CO2 (Carbon Dioxide)
Sn+2 (stannous) Stannic(Sn+4)
2# In neutral or faintly alkaline solution : Reduction half cell : MnO4¯ + 3e- MnO2
Oxidation half cell : I¯(Iodide) IO3¯ (Iodate) , Sulphite(SO32¯) sulphate(SO42¯)
 TOP-20 --PREVIOUS YEAR QUESTIONS OF d-BLOCK REACTIONS( MUST DO …)
Sl Complete and write the balanced Year Sl Complete and write the balanced Ye
no chemical equation no chemical equation ar
1 MnO4¯ +C2O4 ¯+ H 
2 + 11 MnO2 +KOH+ O2
2 KMnO4 +Heat  12 FeCr2O4 + Na2CO3 +O2 
3 Cr2O7 ¯+H2S + H 
2 + 13 MnO4¯ +SO32 ¯+ H+
4 MnO42¯ + H+ 14 Cr2O7 2 ¯+I¯ + H+
5 Na2CrO4 + H+ → 15 Cr2O7 2 ¯+14 H++ 6e-

6 Cr2O7 2 ¯+ OH¯ 16 MnO4¯ +NO2¯ + H+

7 MnO4¯ + H+ +3e¯  17 MnO4¯ +S2 ¯+ H+
8 Cu2+ + I¯  18 MnO4¯ +MnO2 +H2O
9 Cr2O7 2 ¯+Fe2+ + H+ 19 MnO4¯ +S2O32- +H2O
10 Mn2+ 5S2O82- + 8H2O  20 MnO4¯ + I¯ + H2O