K V NO 1 BHUBANESWAR , FREQUENTLY ASKED QUESTIONS –d and f- BLOCK ELEMENTS

A K PANDA , PRINCIPAL K V NO 1 BBSR

Q.1# Why Zn ,Cd, Ans—They do not have unpaired d-electrons in the ground state as well as in their
and Hg are common oxidation states.
normally not **The electronic configurations of Zn, Cd and Hg are represented by the general formula
considered as (n-1)d10ns2. The orbitals in these elements are completely filled in the ground state as well as
Transition metals. in their common oxidation states. Therefore, they are not regarded as transition elements.

Q.2# Transition elements Ans--due to very little energy difference of energy between (n-1)d and ns
show variable oxidation orbitals.
states. Write all the The tendency to take part ‘(n-1)d’ as well as outermost ‘ns’-electrons in
possible O.S. of an bond formation –**When ns electron participate in bonding—Low O.S and when (n-
element (Z=25) 1)d and ns take part in bonding—Higher OS results
Q.3# Transition Ans-- Because of large number of unpaired d-electrons in their atoms they have
metals have high stronger inter-atomic interaction and hence stronger bonding between atoms
boiling points and resulting in higher enthalpies of atomisation.
have high (both metallic and d-d- overlapping of covalent bond )
enthalpies of **One unpaired electron per d orbital is particularly favourable for strong
atomization . 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 .
Q.5# Transition Ans--Due to d-d transition of unpaired d-electron .
metals generally The unpaired electron excited from lower energy d-orbital to higher energy d-orbital(CFT),
from color the energy is absorbed from visible region of radiation and the complementary part of
compound . absorbed light( i.e. reflected light) will decide the colour of the compound
Q.6# Transition Ans-- catalytic activity is ascribed to their
metals and many of 1) ability to adopt multiple oxidation states and
their compound act 2) to form complexes. (form different intermediate with any oxidation states which may
as a good catalyst . lead through lower activation energy path).
(AI-05) ** 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 Ans--This is due to the high (charge / radius) ratio and empty d-orbital .
metals form 1) comparatively smaller sizes of the metal ions,
complex 2) their high ionic charges and
compounds. 3) the availability of empty d orbitals for bond formation.
Q.8 # Transition metal Ans— Because of similar radii and other characteristics of transition metals,
generally form alloys with alloys are readily formed by these metals. Alloys are formed by atoms with
other transition metals. metallic radii that are within about 15 percent of each other. Substitutional and
interstitial alloy
Q.9 # Transition metals Ans-- It because transition metals have voids in their crystal lattice , in which
form a number of small atoms of H , C , N can fit forming interstitial compounds which do not
interstitial compounds have fixed composition . The trapped atoms get bonded to the atoms of TE . e.g. TiC ,
Fe3H , Mn4N
Q. 10 # There is hardly ANS- This is because with increase in atomic number in a series , the increases
any increase in atomic nuclear charge is partly cancelled by the increased shielding effect of electrons in the
size with increasing at.no. d-orbitals of penultimate shell .
in a series of transition
metals .
Q.11# What is Ans-- The overall decrease in atomic and ionic radii from lanthanum to lutetium
lanthanide Cause- due to the imperfect shielding of one f-electron by another in the same
contraction ? State sub-shell. and the dominance of nuclear charge .
the cause and two The extra orbital electrons incompletely shielded the extra nuclear charge.
consequences of Thus effective nuclear charge increases.Thus all the electrons are pulled in closer
lanthanide Consequences—(1) Thus pairs of elements such as Zr/Hf show similar properties like similar ionic
contraction . size.
(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 element to element in the series as compared to 4f –electrons .
than lanthanoid contraction. Why? As because 5f orbitals are comparatively larger and more diffused .
(b)There is a greater range Imperfect screening is greater in case of 5f than in case of 4f .
of oxidation states among the Ans—(b) Due to the fact that 5f, 6d and 7s levels are of comparable
Actinoids 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 Ans—It is due to similar ionic size which is due to lanthanoid contraction . (Due to
Hf show similar the imperfect shielding of one f-electron by another in the same sub-shell.)
properties?

Q.14# The 4d- and 5d-series of transition metals have Ans – Due to lanthanoid contraction
more frequent Metal-Metal bonding in their compounds Due to the imperfect shielding of one f-
than do the 3d-metals . electron by another in the same sub-shell. and
[(OR ,There occurs much more frequent metal-metal bonding the dominance of nuclear charge .
in compounds of heavy transition elements (3rd series).] The extra orbital electrons incompletely shielded the
OR , The metallic radii of 5d and 4d series are nearly the extra nuclear charge.
same . Thus effective nuclear charge increases.Thus all the
OR ,There is a close similarity in physical and chemical electrons are pulled in closer
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 Ans— The reduction potential value depends on relative value of three enthalpies
copper is positive (+0.34V). viz ΔaH0 , ΔiH0 and - ΔhydH0 . The copper has high ΔaH0 and ΔiH0. Therefore high
What is possibly the reason for enthalpy required to transform Cu(s) to Cu2+(aq) is not balanced by its
this? Copper is the only metal in low ΔhydH0 .
the first series of Transition
elements showing this behavior ?
Q.16 # Why is Cr2+ Ans:- Cr2+ is reducing as its configuration changes from d4 to d3 (t2g3 ),
strongly reducing Cr3+ (t2g3 )-- As the having a half-filled t2g level .It has higher CFSE than Mn2+ ( t2g3
3+
and Mn strongly eg2)
oxidising when both On the other hand, the change from Mn3+( d4) to Mn2+ (d5) results in the half-filled (d5)
have d4 configuration which has extra stability.
configuration. ***In aqueous solution Cr3+(t2g3) has more stability than Mn2+ ( t2g3 eg2)
Q.17 # Explain why Cu+ Ans--Cu+ in aqueous solution underoes disproportionation,
ion is not stable in i.e., 2Cu+(aq) → Cu2+(aq) + Cu(s) . Cu ++ is more stable .
aqueous solutions? The E0 value for this is favourable. Cu++ has relatively higher hydration enthalpy
than Cu+

Q.18 # What is When a particular oxidation state of an element becomes less stable relative to other
meant by oxidation state, one lower and one higher, it is said to undergo disproportionation. For
‘disproportionatio example, in aqueous solution:
n’ of an oxidation For example, (i) manganese (VI) becomes unstable relative to manganese(VII) and
state? Give an manganese (IV) in acidic solution.
example (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 Ans— Co(III) has greater tendency to form coordination
following: complexes than Co(II) .
Q.19# Cobalt(II) is stable in aqueous Due to higher charge by radius ratio and also due to greater
solution but in the presence of CFSE
complexing reagents it is easily ( Crystal Field Stabilisation Energy) .Co (III) has d 6 configuration In
oxidised. case of of strong ligand , It is t2g 6 eg0 (stable configuration)
OR ,Co (II) is easily oxidised in the So , Co(II) changes to Co(III) i.e. easily oxidized .
presence of strong ligands.
Q.20# Thed1 Ans-- The ions with d1 configuration have the tendency to lose the only electron present in d-
configuration is subshell to acquire stable d0 configuration (Argon configuration). Hence they are unstable
very unstable in and undergo oxidation and disproportionation .
ions.
Q.21 # Mn+2 Ans-- Mn 3+ + e- ——>Mn 2+
compounds are more (d 4
system , less stable ) (d5 system , more stable )
stable than Fe +2 extra stable due to half-filled conf N
Fe3+ + e-  Fe 2+
toward oxidation to
(d5system , more stable )(d6 system , less stable )
their + 3 state .(AI-06) Cr3+ + e- ——> Cr 2+
OR , Why E0 for Mn+3 / (t2g3 - half filled- more stable )(d4 system , less stable)
Mn+2 couple is more Much larger third Ionisation enthalpy of Mn( where the required change is d 5 to d4) is mainly
positive than for Fe+3 / responsible for this . this also explains why the +3 state of Mn is of little importance
Fe+2 or Cr+3 / Cr+2 . Cr3+ (d3), t2g 3 - half filled ) Higher Crystal Field stabilization energy . (CFSE)
Q.22 # (a) There is no regular Ans— The E0(M2+/M) values are not regular which can be explained from the
0
trend in E values in the series irregular variationof ionization energies (IE1 + IE2) and also the sublimation
Vanadium energy which are relatively much less for Mn and Vanadium. (240kj/mol for
( At No –23) to Copper(At No 29) Mn and 470 KJ/mol for Vanadium)
for M2+/M system..
(ii) EoM2+ /M values are not regular for
first row transition metals (3d series).
Q.23 # How would you account Ans--This is due to the increasing stability of the lower species to which they
for the increasing oxidising are reduced.
power in the series VO2+< Cr2O72–
< MnO4– ?
Q.24 # How would you account for Ans-- Irregular variation of ionisation enthalpies is mainly attributed to
the irregular variation of ionization varying degree of stability of different 3d-configurations (e.g., d0, d5, d10
enthalpies (first and second) in the are exceptionally stable).
first series of the transition
elements?

Q.25 # Why is the highest Ans-- Because of small size and high electronegativity oxygen or
oxidation state of a metal fluorine can oxidise the metal to its highest oxidationstate.
exhibited in its oxide or fluoride **The ability of fluorine to stabilise the highest oxidation state is
only? due to either higher lattice energy as in the case of CoF3, or higher
OR , bond enthalpy terms for the higher covalent compounds, e.g., VF5 and
Although ‘F’ is more electronegative CrF6.
than ‘O’, the highest Mn fluoride is The ability of oxygen to stabilise these high oxidation states exceeds that of
MnF4, whereas the highest oxide is fluorine. The ability of oxygen to form multiple bonds with transition
Mn2O7.—Explain metal explains its superiority.
OR Thus the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.
Why the highest oxidation state is In the covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by O’s
exhibited in oxo-anions of a transition including a Mn–O–Mn bridge.
metal.?
Q.26# Which is a Ans-- Cr2+ is stronger reducing agent than Fe2+
stronger reducing Reason:d4 → d3 occurs in case of Cr2+ to Cr3+ ((t2g3 - half filled- more stable )
2+ 2+
agent Cr or Fe But d6 → d5 occurs in case of Fe2+ to Fe3+ .
and why ? In a medium (like water) d3is more stable (higher CFSE) as compared to d5 .

Q.27 # Why is the E0 value Ans--Much larger third ionisation energy of Mn (where the required change is d5 to
for the Mn3+/Mn2+ couple d4) is mainly responsible for this. This also explains why the +3 state of Mn is of
much more positive than little importance.
that for Cr3+/Cr2+ or Fe3+/Fe2+?
Explain.
Q. 28 # Among lanthanoids , Ln(III) ANS- lanthanoid metals show +2 and +4 O.S to attain
compounds are predominant . However , extra stability of f0 f7 and f14 configuration .
occasionally in solutions or in solid Eu2+ ,Tb4+ -(4f7)-half filled . Ce4+ ( 4f0)
compounds , +2 & +4 ions are also obtained .
Q.29 # How is the variability ANS- In transition elements the oxidation states vary by one
in oxidation states of For example, for Mn it may vary as +2, +3, +4, +5, +6, +7.
transition metals different In the nontransition elements the variation is selective, always differing by 2, e.g.
from that of the non +2, +4, or +3, +5 or +4, +6 etc.
transition metals? Illustrate
with examples.
Q. 30 # Why there is general ANS- The decrease in metallic radius coupled with increase in atomic mass
increase in density from Ti to results in a general increase in density .
Cu .
Q. 31 # The higher O.S are ANS- Due to presence of maximum number of unpaired electrons in a TM
usually exhibited by the which is present in the middle of the series .
members in the middle of the
series of Transition Elements.
Q. 32 # Mn2+ is ANS-Mn2+(d5 , half-filled ) is stabler than Mn3+(d4) , so Mn2+ not easily get oxidized
much more Fe2+(d6) is less stable than Fe3+ (d5 , half-filled) . so Fe2+ is easily get oxidized to get stable
resistant thanFe2+ configuration .
towards oxidation .
Q.38 #.Why is HCl not used to acidify a Ans-Since Clˉ of Hydrochloric acid is oxidized to chlorine by
permanganate solutions in volumetric MnO4ˉ . so , actual amount of KMnO4 required to oxidize
estimation of Fe+2 or C2O42‾ . C2O42‾couldnot be 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+2compounds 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 required
more positive than for Fe+3 / Fe+2 change is d5 to d4) is mainly responsible for this . this also explains why
+3 +2
or Cr / Cr . the +3 state of Mn is of little importance .

Q.35 # Why do Ans-- the high enthalpy of hydration of transition elements is due to
transition (i) small size of the cation and
elements have (ii) large positive charge e.g. Cu++ has higher enthalpy of hydration than Cu+
high enthalpy of
hydration?

Q.36 # For the first row transition metals the Eo values are: Ans--The E0 (M2+/M) values are not regular which
Eo V Cr Mn Fe Co Ni Cu can be explained from the irregular variation of
M2+/M) -1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 ionisation enthalpies ( Δi H1+Δ iH2) and also the
+0.34 -------- Explain the irregularity in the above sublimation enthalpies which are relatively much
values. less for Mn and V..

Q. 37 # What are Ans- Alloys may be homogeneous solid solutions in which the atoms of one metal are
alloys? Name an distributed randomly among the atoms of the other
important alloy which
contains some of the A well known alloy is mischmetallwhich consists of a lanthanoid metal (~ 95%) and iron (~
lanthanoid metals. 5%) and traces of S, C, Ca and Al.
Mention its uses. A good deal of mischmetall is used in Mg-based alloy to produce bullets, shell and lighter
OR , Write two flint.
uses of mischmetall
Q.38 # What is the Ans- It will change to yellow colour by forming Potassium chromate
effect of increasing ( in alkaline medium)
pH on a solution of K2Cr2O7 ( orange) ------ ( OH-)K2CrO4 ( Yellow)
K2Cr2O7 ** K2CrO4 ( Yellow) ------ ( H+)-K2Cr2O7 ( orange)
Q.39# W h a t chemical changes takes places w h e n – Ans (i) Potassium manganate (K2MnO4 –green ,
(i) Pyrolusite is fused with KOH in the presence of air paramagnetic)
(ii) Chromite ore is fused with molten NaOH in presence (ii) Pottasium Chromate (K2CrO4 – Yellow ,
of air diamagnetic)
(iii)When a solution of chromate is acidified (iii) K2Cr2O7 – Orange )
(iv)NH3 is added to a suspension of AgCl (iv) (iv) Soluble complex , [Ag(NH3)2]Cl
(v) Alkaline KMnO4 reacts with KI (v) (v) Iodate (IO3¯ ) and Mn2+
Q.40# Which is the last element in the series of the Ans :-Lawrencium(103)
actinoids? Write the electronic configuration of this 5f 146d17s2
element. Comment on the possible oxidation state of this +3
element.
Q.41 # On what ground can you Ans--On the basis of incompletely filled 3d orbitals in case of scandium atom in
say that scandium (Z = 21) is a its ground state (3d1), it is regarded as a transition element. On the other hand,
transition element but zinc (Z = zinc atom has completely filled d orbitals (3d10) in its ground state as well as in
30) is not? its oxidisedstate, hence it is not regarded as a transition element.
Q.42# Silver atom has completely filled d Ans--Silver (Z = 47) can exhibit +2 oxidation state wherein it will
orbitals (4d10) in its ground state. How have incompletely filled d-orbitals (4d), hence a transition element.
can you say that it is a transition
element?
Q.43 # In the series Sc (Z = 21) Ans- In the formation of metallic bonds, no eletrons from 3d-orbitals are
to Zn (Z = 30), the enthalpy of involved in case of zinc, while in all other metals of the 3d series,
atomization of zinc is the electrons from the d-orbitals are always involved in the formation of
lowest, i.e., 126 kJ mol–1. Why? metallic bonds.
Q.44 # Name a transition Ans--Scandium (Z = 21) does not exhibit variable oxidation states.
element which does not Only oxidation states i.e Sc3+
exhibit variable 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 series number of unpaired electrons. i.e five ( +2 , +3 , +4 , +5 , +6 ,
of transition metals from Sc (Z = 21) to Zn (Z = +7)
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 will
moment of a divalent ion in aqueous have d5 configuration (five unpaired electrons). The magnetic moment, μ
solution if its atomic number is 25. 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 (b) Eu . Eu2+ is formed by losing the two s- electrons and its Xe]
to 4f7 accounts for its formation .
(a) exhibit +4 oxidation state. (AI14)
(b) exhibit +2 oxidation state. (D-14)
Q.49 # Among the species Ans--In all the above ion the most stable oxidising state is +3 .therefore
Sc3+,.Ce4+, and Eu2+ which one is Sc3+ will remain unchanged. Ce4+has the tendency to accept one electron to
good oxidising agent ? get the +3 oxidation state. Hence Ce4+ is a good oxidising agent.Eu2+ has
3+ 0 0
Sc ——>[A r] 3d 4s the tendency to lose one electron to get the +3 oxidation state. Hence Eu2+
4+ 0 0 0
Ce ——> [Xe] 4f 5d 6s is a good reducing agent.
Eu2+ ——>[Xe] 4f75d0 6s0
Q.50 # Mn (III) undergoes Ans : Mn (III) unstable oxidation states , it undergoes disproportionation to
disproportionation reaction Mn2+ and MnO2 ( +4 oxidation states )
easily.
51 # Out of Mn3+ and Cr3+ , Ans :- Mn3+ (3d4 4s0 , four unpaired d- electrons ) -- more paramagnetic -
which is more paramagnetic and higher no. of unpaired d- electrons Cr3+( 3d3 4s0 , three unpaired electron)
why ?
52# Which transition Ans :- Cu . The sum of high enthalpy of atomization and ionization enthalpy to
metal of 3d series has transform Cu(s) Cu2+(aq) is not balanced by hydration enthalpy .
positive E0(M2+/M)
value and why

53 # Sc3+ is Ans :-Sc3+ have no unpaired d- electron . No d—d transition of unpaired d-electron . BUT
colourless in aqueous Ti3+ have one unpaired d- electron .d—d transition of unpaired d-electron in visible region
solution whereas Ti3+ . The complementary colour is seen .
is coloured (2014-F)
54# La3+ (Z = 57) and Ans: La3+ : (Xe] 4f0 and Lu3+ (Xe] 4f14 - absence of unpaired f- electrons for f—f
Lu3+ (Z = 71) do not transition . so no f—f transition in the visible region .
show any colour in
solutions.
55# Compare actinoids and lanthanoids with special (i) In Lanthanoids electrons are filled in
reference to their : antepenultimate shell i.e 4f subshell BUT in Actinoids
(i) electronic configurations of atoms 5f subshell
(ii) oxidation states of elements (ii) +3 , +2 and +4 ( do not show greater range of O .S
(iii) general chemical reactivity of elements. ) BUT in Actinoids +3 , +4 , +5, +6 &7
(iv) atomic and ionic sizes (iiI) Lanthanoids are less reactive whereas
Actinoids( low I.E) are more reactive chemically
(iv) Lanthanoids are smaller than the actinoids .
Q.56 # Calculate the number of unpaired Mn2+ = 5 , Cr3+ = 3 , V3+ = 2 , Fe2+ = 4
electrons in the following gaseous state ions: Cr3+ , due to half-filled configuration
2+ 3+ 3+ 2+
Mn , Cr , V and Fe ( 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 are Cations are coloured in aqueous solutions:- V 3+ (d1- )1-unpaired
coloured in aqueous solutions and why? electron, Mn2+(d5) - 5 unpaired electron ,Ti3+(d1) - 1 unpaired electron,
3+ 3+ 4+ 2+ 3+ + 3+
Sc , V , Ti , Mn ,Ti , Cu , Fe and Fe3+(d5- 5 unpaired electron) and Co2+(d7) - 3 unpaired electron. Due
Co2+. to d-d transition of unpaired d- electrons
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 Atomic size decreases from Ti to Cu .
increase in density of elements REASON:-Along a period ( 3d – series) Relative increase in nuclear charge is more
from titanium (Z = 22) to dominant than relative increase in screening effect in d- subshell( imperfect
copper (Z = 29) in the first screening)
series of transition elements. Atomic mass increases but volume decreases that’s why density increases from
Ti to Cu .
Q.60# The higher oxidation Due to the presence of higher number of unpaired electrons.
states are usually exhibited by (Mn shows O.S from +2 to +7)—present in the middle of the series .
the members in the middle of a
series of transition elements.
Q.61# There is a greater horizontal similarity in Atomic sizes are very close by along the d- series
the properties of the transition elements than of
the main group elements.
Q.62# The third ionization enthalpy Due to half –filled configuration.( extra stable- ) Removing third
of manganese (Z = 25) is electron from Mn2+ needs high I.E ( tightly held)
exceptionally high.
Q.63# Discuss the relative stability Mn-- 3d5 4s 2
in aqueous solutions of +2 oxidation Due to half –filled configuration.( extra stable- )-- Mn2+ - -- 3d54s0
state among the elements : Cr,Mn, Cr--3d 5 4s 1 ; Cr2+--3d 4 4s 0 (unstable)
Fe and Co. How would you justify Cr3+ , Stable-due to half-filled configuration – Stable O.S. In aq.
this situation? (At. Nos. Cr = 24, Mn Solution
= 25, Fe = 26, Co = 27) ( t2g3 eg0 ----- Higher crystal field stabilization energy ) CFT
Co--3d 7 4s 2 ; Co2+--3d 7 4s 0 (unstable)
Fe --3d 4s ; Fe++- 3d 6 4s0(unstable)
6 2
Q.64 # What may be the possible oxidation 3d 3 4s 2--- (+2 ,+3 ,+5- stable)
states of the transition metals with the following d 3d5 4s 2---( +2 , +3 , +4 , +5 , +6 , +7)
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
series of transition elements, manganese exhibits ( i.e 5 ) [ 3d5 4s0 ]
the maximum paramagnetism.
Q.66 # Mn3+ is a Mn (II) stable – d5 configuration . (-half filled configuration- stable) . So Mn (III) being
good oxidising agent unstable get itself reduced to stable Mn(II) and act as oxidizing agent .
1 0 2
Q.67 # Give reason (i) 57La—[Xe]54 4f 5d 6s ; 57La3+—[Xe]54 4f05d06s0 -- fulfilled configurtaion
(i) The +3 oxidation state of 57La , 64Gd--- —[Xe]54 4f75d16s2 ; 64Gd3+--- —[Xe]54 4f75d06s0 -half –filled
14 1 2 3+
64Gd , 71Lu are especially stable . 71Lu----—[Xe]54 4f 5d 6s ; 71Lu ----—[Xe]54 4f145d06s0- fulfilled configuration
(ii) Ce3+ can be easily oxidized to (ii)Due to fulfilled configuration of Ce4+ - (Noble gas configuration-
Ce4+ Configuration of Xe) –stable . Ce3+ can be easily oxidized to Ce4+

Q.68# What are the 1. High enthalpy of atomization. 2. Show paramagnetism 3. Show colour
characteristics of the transition compounds 4. Complex formation ability 5 . Show variable oxidation
elements and why are they states .etc …( unique properties of Transitional metals)
called transition elements? 2. They show transitional characteristics between s- block and p- block
elements .
Q.69 # What are the different oxidation +3 ( commonOxidatyion States) +2 and +4 are also seen
states exhibited by the lanthanoids? due to half –filled and fulfilled configuration of various ions.
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 as ground state or in their commonly found Oxidation states .
the transition elements?
Q.71 # Name the oxometal anions of the first series of Permanganate ( MnO4 ¯ ) , +7-- Oxidation state ,
the transition metals in which the metal exhibits the Mn belongs to 7th group .
oxidation state equal to its group number.
Q.72 # How is the variability in oxidation Oxidation states in Transition metals differs by one
states of transition metals different from BUT , in Non- transition metals O.S differs by 2
that of the non transition metals? Illustrate Phosphorous - +3 and +5 ( as in P2O3 and P2O5 )
with examples. Iron – Fe2+ and Fe3+
Q.73 # What are Ans-- It because transition metals have voids in their crystal lattice , in which small
interstitial atoms of H , C , N can fit forming interstitial compounds which do not have fixed
compounds? Why are composition . The trapped atoms get bonded to the atoms of TE .e.g. TiC , Fe 3H , Mn4N ,VH0.56
such compounds well TiH1.7 .
known for transition ** Due to variable O.s of Transition metals , Metal deficient defects are seen in solid state
metals? 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 oxidation states Mn-- 3d5 4s 2Mn2+ - -- 3d54s0(half –filled )
in the first series of the transition elements? Illustrate Zn --3d10 4s 2, Zn++ --3d10 4s 0 (fulfilled configuration)
your answer with examples.
Q.75 # Write down the Hydrated ions (octahedral)–water is the ligand ( weak field – high spin complex ) Δ 0< P
number of 3d electrons in each Ti2+ ----(2 unpaired d- elctrons)3d24s0--- t2g2eg0
of the following ions: Ti2+, V2+, V2+--(3 unpaired d- elctrons)--3d34s0---- t2g3eg0
3+ 2+ 2+ 3+
Cr , Mn , Fe , Fe , Co , Ni 2+ 2+ Cr3+--(3 unpaired d- elctrons)-3d34s0------ t2g3eg0
2+
and Cu . Indicate how would Mn2+-(5 unpaired d- elctrons)3d54s0-- t2g3eg2
2+ 6 0 4 2
you expect the five 3d orbitals to Fe --(4 unpaired d- elctrons)-3d 4s - t2g eg
be occupied for these hydrated Fe --(5 unpaired d- elctrons)-3d 4s -- t2g eg2
3+ 5 0 3

ions (octahedral). Co2+---(3 unpaired d- elctrons)-3d74s0-- t2g5eg2

Ni2+---(2 unpaired d- elctrons)-3d84s0-- t2g8eg2
Cu2+---(1 unpaired d- elctrons)3d94s0-- t2g6eg3
Example Magnetic Magnetic moment depends on spin and orbital motion of negatively charged unpaired
Moment (BM) electron .by knowing magnetic value we can predict the number of unpaired d-
K4[Mn(CN)6] 2.2 electron(s).
[Fe(H2O)6]2+ 5.3 Spin –only formula , µ = [n(n+2)]1/2 = [1(1+2)]1/2 = 1.73 BM (example)
K2[MnCl4] 5.9 Example Magnetic No.of configuration
Q.76 # What can be inferred Moment(B unpaired
from the magnetic moment M) electron
values of the following K4[Mn(CN)6] 2.2 1 t2g5eg0 (Strong Oh--CFT
complex species ? field)
[Fe(H2O)6]2+ 5.3 4 t2g4eg2 (weak field)
K2[MnCl4] 5.9 5 eg2t2g3(weak field)
Q.77 # Write the electronic configurations of Atomic numbers 61--[Xe]544f 5d0 6s 2
5

the elements with the atomic numbers 61, 91, Atomic numbers 91--[Rn]86 5f 26d17s 2
101, and 109. Atomic numbers 101-[Rn]86 5f 136d07s 2
 Atomic numbers 109 ---[Rn]86 5f 146d77s 2
Q.78# What are inner transition elements? Lanthanoids ( 4f – series from 6th period and 3rd group) and
Decide which of the following At.nos are of actinoids( 5f – series from 7th period and 3rd group) are known as Inner
the inner transition elements :29, 59, 74, 95, transition elements :
102, 104. Lanthanoids-- 59 Actinoids-- 95, 102
Q.79 # Sm2+ , Eu2+ and ** Sm+2(f 7) ,Eu+2(f 7),Yb+2(f 14) Sm+3,Eu+3, Yb+3 ( Stable , common O.S)
Yb+2 ions in solutions are (Sm2+ , Eu2+ and Yb+2 ions tendency to change into +3 O.S.)-- [ Acts as reducing
good reducing agents but an agent)
aq. 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 configurations of two Xe is the noble gas core whose atomic number is 54
members of the lanthnoid series are as follows : 4f 1 [Xe]544f1 5d 1 6s 2-- Atomic number is 58 ; stable O.S . +4
5d 1 6s 2 and 4f 7 5d 0 6s 2 . What are their atomic (empty conf.)
numbers?Predict the Oxidation States exhibited by [Xe]544f7 5d 0 6s 2-- Atomic number is 63 ; stable O.S +2
these elements in their compounds . (AI-05) (half-filled conf.)
1 0 0
Q.81 # Use Hund’s rule to derive the electronic 58Ce—[Xe]54 4f 5d 6s Only one unpaired electron is present
configuration of Ce3+ ion, and calculate its magnetic Spin –only formula , µ = [n(n+2)]1/2 = [1(1+2)]1/2 = 1.73
moment on the basis of ‘spin-only’ formula. BM

Preparation , properties and uses of

Potassium dichromate K2Cr2O7 and Potassium permanganate KMnO4
Describe the preparation of potassium dichromate from iron Describe the preparation of Potassium permanganate KMnO4
chromite ore.
Potassium dichromate K2Cr2O7 – Preparation , and uses Potassium permanganate KMnO4- Preparation , and uses
STEP-1: Fusion of chromite ore (FeCr2O4) with sodium
potassium carbonate in free access of air ( Alkaline Oxidation) Potassium permanganate is prepared by fusion of MnO2 with an
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2 alkali metal hydroxide and an oxidising agent like KNO3. This
STEP-2:The yellow solution of sodium chromate is filtered and produces the dark green K2MnO4 which disproportionates in a
acidified with sulphuric acid to give a solution from which neutral or acidicsolution to give permanganate.
orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised. STEP-1 : 2MnO2 + 4KOH + O2 → 2K2MnO4 (dark green)+
2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O 2H2O
***Sodium dichromate is more soluble than potassium STEP-2 :3MnO42– + 4H+ → 2MnO4– (dark purple or almost
dichromate. black crystals)+ MnO2 + 2H2O
STEP-3:Potassium dichromate is therefore, prepared by Commercially it is prepared by the alkaline oxidative fusion of
treating the solution of sodium dichromate with potassium MnO2 followed by the electrolytic oxidation of manganate (Vl).
chloride. STEP-1 : MnO2 ( fused with KOH, oxidized with air or KNO3)
Na2Cr2O7 + 2 KCl → K2 Cr2O7 (Orange crystals crystallise out.)  MnO42– (manganate ion)
+ 2 NaCl STEP-2 :MnO42– (manganate ion) on Electrolytic oxidation in
**The chromates and dichromates are interconvertible in alkaline solution  MnO4– ( permanganate ion)
aqueous solution depending upon pH of the solution. The KMnO4 is used as (1) a strong oxidant use in labs and industry
oxidation state of chromium in chromate and dichromate is the as volumetric reagent in alkaline and acidic media
same. (2) Disinfectant for well water
2 CrO42– + 2H+ → Cr2O72– + H2O (3) as bleaching agent for wood ,cotton ,silk and other textiles.
Cr2O72– + 2 OH- → 2 CrO42-
USES: K2Cr2O7 is used as (1) primary standard in 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 :MnO4ˉ (permanganate) +8H+ + 5e-  Mn+2(manganous) + 4 H2O
Cr2O72ˉ (dichromate) + 14H+ + 6e- 2Cr+3 +7H2O
Oxidation half cell : Iˉ(Iodide) I2 (Iodine) , S 2ˉ (Sulphide) S(Sulphur) ,
Sulphite(SO32ˉ) sulphate(SO42ˉ) , Nitrite (NO2ˉ ) Nitrate (NO3ˉ )
Fe+2(Ferrous)  Fe+3 (Ferric) , C2O42 ˉ(oxalate)  CO2 (Carbon Dioxide)
Sn (stannous) Stannic(Sn )
+2 +4

2# In neutral or faintly alkaline solution : Reduction half cell : MnO 4ˉ + 3e- MnO2
Oxidation half cell : Iˉ(Iodide) IO3ˉ (Iodate) , Sulphite(SO32ˉ) sulphate(SO42ˉ)

TOP-20 --PREVIOUS YEAR QUESTIONS OF d-BLOCK REACTIONS( MUST DO …)

Sl Complete and write the balanced Yea Sl Complete and write the balanced Ye
no chemical equation r no chemical equation ar
1 MnO4¯ +C2O42 ¯+ H+ 11 MnO2 +KOH+ O2
2 KMnO4 +Heat  12 FeCr2O4 + Na2CO3 +O2 
3 Cr2O7 2 ¯+H2S + H+ 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