CHAPTER 8 – d and f- block elements

PREVIOUS YEAR QUESTION PAPERS – 2008 TO 2020 – SOLVED

Q.1# Why Zn ,Cd, and Hg Ans—They do not have unpaired d-electrons in the ground state as well as in their common oxidation states.
are normally not **The electronic configurations of Zn, Cd and Hg are represented by the general formula (n-1)d10ns2. The orbitals in
considered as Transition these elements are completely filled in the ground state as well as in their common oxidation states. Therefore,
metals. 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 orbitals.
show variable oxidation The tendency to take part ‘(n-1)d’ as well as outermost ‘ns’-electrons in bond formation –**When ns electron
states.Write all the participate in bonding—Low O.S and when (n-1)d and ns take part in bonding—Higher OS results
possible O.S. of an element
(Z=25)

Q.3# Transition metals Ans-- Because of large number of unpaired d-electrons in their atoms they have stronger inter-atomic interaction
have high boiling points and hence stronger bonding between atoms resulting in higher enthalpies of atomisation.
and have high enthalpies (both metallic and d-d- overlapping of covalent bond )
of atomization . (AI-05) **One unpaired electron per d orbital is particularly favourable for strong interatomic interaction

Q.4# Transition metals and many of their Ans—Due to spin and orbital motion of negatively charged unpaired d-electron(s) in an
compounds show paramagnetic behaviour . atom ,ion or molecule
(AI-05)
Q.5# Transition metals Ans--Due to d-d transition of unpaired d-electron .
generally from color The unpaired electron excited from lower energy d-orbital to higher energy d-orbital(CFT), the energy is absorbed
compound (AI-08) 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 Ans-- catalytic activity is ascribed to their
many of their compound 1) ability to adopt multiple oxidation states and
act as a good catalyst . (AI- 2) to form complexes. (form different intermediate with any oxidation states which may lead through lower
05) 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 Ans--This is due to the high (charge / radius) ratio and empty d-orbital .
form complex compounds. 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 Ans— Because of similar radii and other characteristics of transition metals, alloys are readily formed by these
generally form alloys with metals. Alloys are formed by atoms with metallic radii that are within about 15 percent of each other.
other transition metals. Substitutional and interstitial alloy .

Q.9 # Transition metals form a Ans-- It because transition metals have voids in their crystal lattice , in which small atoms of H , C , N
number of interstitial compounds 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 ANS- This is because with increase in atomic number in a series , the increases nuclear charge is partly
in atomic size with increasing at.no. cancelled by the increased shielding effect of electrons in the d-orbitals of penultimate shell .
in a series of transition metals .
Q.11# What is lanthanide Ans-- The overall decrease in atomic and ionic radii from lanthanum to lutetium
contraction ? State the Cause- due to the imperfect shielding of one f-electron by another in the same sub-shell. and the dominance of
cause and two nuclear charge .
consequences of The extra orbital electrons incompletely shielded the extra nuclear charge.
lanthanide contraction . 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 greater from Ans—(a) The 5f electrons themselves provide poor shielding from element to element in the
element to element than lanthanoid series as compared to 4f –electrons .
contraction. Why? As because 5f orbitals are comparatively larger and more diffused . Imperfect screening is
(b)There is a greater range of oxidation greater in case of 5f than in case of 4f .
states among the Actinoids than that in Ans—(b) Due to the fact that 5f, 6d and 7s levels are of comparable energiesi.e the energy
Lanthanoids differences are very less , so electron can participate from all three sub-shells .

Q.13 # WhyZr and Hf show Ans—It is due to similar ionic size which is due to lanthanoid contraction . (Due to the imperfect shielding of one
similar properties? f-electron by another in the same sub-shell.)
Q.14# The 4d- and 5d-series of transition metals have more frequent Metal- Ans – Due to lanthanoid contraction
Metal bonding in their compounds than do the 3d-metals . Due to the imperfect shielding of one f-electron by another in
[(OR ,There occurs much more frequent metal-metal bonding in compounds the same sub-shell. and the dominance of nuclear charge .
of heavy transition elements (3rd series).] The extra orbital electrons incompletely shielded the extra
OR , The metallic radii of 5d and 4d series are nearly the same . nuclear charge.
OR ,There is a close similarity in physical and chemical properties of the 4 d Thus effective nuclear charge increases.Thus all the electrons are
and 5 d series of the pulled in closer
transition elements, much more than expected on the basis of usual family
relationship.
Q.15 # The E0(M2+/M) value for copper is Ans— The reduction potential value depends on relative value of three enthalpies viz ΔaH0 , ΔiH0 and
positive (+0.34V). - ΔhydH0 . The copper has high ΔaH0 and ΔiH0. Therefore high enthalpy required to transform Cu(s) to
What is possibly the reason for this? Cu2+(aq) is not balanced by its low ΔhydH0 .
Copper is the only metal in the first series
of Transition elements showing this
behavior ?
Q.16 # Why is Cr2+ strongly Ans:- Cr2+ is reducing as its configuration changes from d4 to d3 (t2g3 ),
reducing and Mn3+ strongly Cr3+ (t2g3 )-- As the having a half-filled t2g level .It has higher CFSE than Mn2+ ( t2g3 eg2)
oxidising when both have On the other hand, the change from Mn3+( d4) to Mn2+ (d5) results in the half-filled (d5) configuration which has
d4 configuration. 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 stable relative to other oxidation state, one lower
‘disproportionation’ of and one higher, it is said to undergo disproportionation. For example, in aqueous solution:
an oxidation state? Give For example, (i) manganese (VI) becomes unstable relative to manganese(VII) and manganese (IV) in acidic
an example 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 complexes than Co(II) .
Q.19# Cobalt(II) is stable in aqueous solution but in the Due to higher charge by radius ratio and also due to greater CFSE
presence of complexing reagents it is easily oxidised. ( Crystal Field Stabilisation Energy) .Co (III) has d 6 configuration In case of of strong
OR ,Co (II) is easily oxidised in the presence of strong ligand , It is t2g 6 eg0 (stable configuration)
ligands. So , Co(II) changes to Co(III) i.e. easily oxidized .
Q.20# Thed1 configuration Ans-- The ions with d1 configuration have the tendency to lose the only electron present in d-subshell to acquire
is very unstable in ions. stable d0 configuration (Argon configuration). Hence they are unstable and undergo oxidation and
disproportionation .
Q.21 # Mn+2 compounds Ans-- Mn 3+ + e- ——>Mn 2+
4 system , less stable ) 5 system , more stable )
are more stable than Fe +2 (d (d
toward oxidation to their extra stable due to half-filled confN
+ 3 state .(AI-06) Fe3+ + e- → Fe 2+
5system , more stable )(d6 system , less stable )
0
OR , Why E for Mn / +3 (d
Mn+2 couple is more Cr3+ + e- ——> Cr 2+
3 - half filled- more stable )(d4 system , less stable)
positive than for Fe+3 / (t2g
Much larger third Ionisation enthalpy of Mn( where the required change is d5 to d4) is mainly responsible for this .
Fe+2 or Cr+3 / Cr+2 .
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 E 0 values in the series Ans— The E0(M2+/M) values are not regular which can be explained from
2+
Vanadium ( At No –23) to Copper(At No 29) for M /M system.. the irregular variationof ionization energies (IE1 + IE2) and also the
(ii) EoM2+ /M values are not regular for first row transition metals (3d sublimation energy which are relatively much less for Mn and Vanadium.
series). (240kj/mol for Mn and 470 KJ/mol for Vanadium)
Q.23 # How would you account for the increasing oxidising Ans--This is due to the increasing stability of the lower species to which they are
power in the series VO2+< Cr2O72–< MnO4– ? reduced.
Q.24 # How would you account for the irregular Ans-- Irregular variation of ionisation enthalpies is mainly attributed to varying degree of
variation of ionization enthalpies (first and second) stability of different 3d-configurations (e.g., d0, d5, d10 are exceptionally stable).
in the first series of the transition elements?
Q.25 # Why is the highest oxidation state of a Ans-- Because of small size and high electronegativity oxygen or fluorine can oxidise the
metal exhibited in its oxide or fluoride only? metal to its highest oxidationstate.
OR , **The ability of fluorine to stabilise the highest oxidation state is
Although ‘F’ is more electronegative than ‘O’, due to either higher lattice energy as in the case of CoF3, or higher bond enthalpy terms for
the highest Mn fluoride is MnF 4, whereas the the higher covalent compounds, e.g., VF5 and CrF6.
highest oxide is Mn2O7.—Explain The ability of oxygen to stabilise these high oxidation states exceeds that of fluorine. The ability
OR of oxygen to form multiple bonds with transition metal explains its superiority.
Why the highest oxidation state is exhibited in Thus the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.
oxo-anions of a transition 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 Ans-- Cr2+ is stronger reducing agent than Fe2+
reducing agent Cr2+ or Reason:d4 → d3 occurs in case of Cr2+ to Cr3+ ((t2g3 - half filled- more stable )
Fe2+ and why ?
 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 the Mn3+/Mn2+ couple Ans--Much larger third ionisation energy of Mn (where the required change is d5 to
much more positive than that for Cr3+/Cr2+ or Fe3+/Fe2+? d4) is mainly responsible for this. This also explains why the +3 state of Mn is of little
Explain. importance.
Q. 28 # Among lanthanoids , Ln(III) compounds are ANS- lanthanoid metals show +2 and +4 O.S to attain extra stability of f0 f7
predominant . However , occasionally in solutions or in solid and f14 configuration .
compounds , +2 & +4 ions are also obtained . Eu2+ ,Tb4+ -(4f7)-half filled . Ce4+ ( 4f0)
Q.29 # How is the variability in oxidation ANS- In transition elements the oxidation states vary by one
states of transition metals different from For example, for Mn it may vary as +2, +3, +4, +5, +6, +7.
that of the non transition metals? In the nontransition elements the variation is selective, always differing by 2, e.g. +2, +4, or +3, +5 or
Illustrate with examples. +4, +6 etc.
Q. 30 # Why there is general increase in ANS- The decrease in metallic radius coupled with increase in atomic mass results in a general
density from Ti to Cu . increase in density .
Q. 31 # The higher O.S are usually ANS- Due to presence of maximum number of unpaired electrons in a TM which is present in the
exhibited by the members in the middle of middle of the series .
the series of Transition Elements.
Q. 32 # Mn2+ is much more ANS-Mn2+(d5 , half-filled ) is stabler than Mn3+(d4) , so Mn2+ not easily get oxidized
resistant than Fe2+ Fe2+(d6) is less stable than Fe3+ (d5 , half-filled) . so Fe2+ is easily get oxidized to get stable configuration .
towards oxidation .
Q.38 #.Why is HCl not used to acidify a Ans-Since Clˉ of Hydrochloric acid is oxidized to chlorine by MnO 4ˉ . so , actual amount of
permanganate solutions in volumetric KMnO4 required to oxidize C2O42‾couldnot be determined
estimation of Fe+2 or C2O42‾
Q.33 # Give reason for it?. Ni+2 compounds are thermodynamically Ans--The oxidation state of Pt in K2 Pt Cl6is +4 .The sum of the first
more stable than Pt+2compounds whilstPt(IV) are relatively more stable four ionization energies (IE1+IE2 +IE 3+IE 4) of pt is less than those of
than Ni(IV) compounds . OR, K2PtCl6 is well known cpds. but Ni.
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 change is d 5 to d4) is mainly
more positive than for Fe+3 / Fe+2 responsible for this . this also explains why the +3 state of Mn is of little importance .
or Cr+3 / Cr+2 .
Q.35 # Why do Ans-- the high enthalpy of hydration of transition elements is due to
transition elements have (i) small size of the cation and
high enthalpy of (ii) large positive charge e.g. Cu++ has higher enthalpy of hydration than Cu+
hydration?
Q.36 # For the first row transition metals the Eo values are: Ans--The E0 (M2+/M) values are not regular which can be
o
E V Cr Mn Fe Co Ni Cu explained from the irregular variation of ionisation
M2+/M) -1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 +0.34 -------- Explain enthalpies ( Δi H1+Δ iH2) and also the sublimation enthalpies
the irregularity in the above values. which are relatively much less for Mn and V..
Q. 37 # What are alloys? Ans- Alloys may be homogeneous solid solutions in which the atoms of one metal are distributed randomly among
Name an important alloy the atoms of the other
which contains some of the A well known alloy is mischmetallwhich consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca
lanthanoid metals. Mention and Al.
its uses. OR , Write two A good deal of mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint.
uses of mischmetall
Q.38 # What is the effect of Ans- It will change to yellow colour by forming Potassium chromate
increasing pH on a solution ( in alkaline medium)
of K2Cr2O7 K2Cr2O7 ( orange) ------ ( OH-)→K2CrO4 ( Yellow)
** 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 , paramagnetic)
(i) Pyrolusite is fused with KOH in the presence of air (ii) Pottasium Chromate (K2CrO4 – Yellow , diamagnetic)
(ii) Chromite ore is fused with molten NaOH in presence of air (iii) K2Cr2O7 – Orange )
(iii)When a solution of chromate is acidified (iv) (iv) Soluble complex , [Ag(NH3)2]Cl
(iv)NH3 is added to a suspension of AgCl (v) (v) Iodate (IO3¯ ) and Mn2+
(v) Alkaline KMnO4 reacts with KI
Q.40# Which is the last element in the series of the actinoids? Write the electronic configuration of Ans :-Lawrencium(103)
this element. Comment on the possible oxidation state of this element. 5f 146d17s2
+3
Q.41 # On what ground can Ans--On the basis of incompletely filled 3d orbitals in case of scandium atom in its ground state (3d1), it is regarded
you say that scandium (Z = as a transition element. On the other hand, zinc atom has completely filled d orbitals (3d10) in its ground state as
21) is a transition element well as in its oxidized state, hence it is not regarded as a transition element.
but zinc (Z = 30) is not?
Q.42# Silver atom has completely filled d orbitals (4d10) in its Ans--Silver (Z = 47) can exhibit +2 oxidation state wherein it will have
ground state. How can you say that it is a transition element? incompletely filled d-orbitals (4d), hence a transition element.
Q.43 # In the series Sc (Z = 21) to Zn (Z = 30), Ans- In the formation of metallic bonds, no eletrons from 3d-orbitals are involved in case of
the enthalpy of atomization of zinc is the zinc, while in all other metals of the 3d series, electrons from the d-orbitals are always
lowest, i.e., 126 kJ mol–1. Why? involved in the formation of metallic bonds.
Q.44 # Name a transition element which does Ans--Scandium (Z = 21) does not exhibit variable oxidation states. Only oxidation states i.e Sc3+
not exhibit variable oxidation states.
45# Name the element showing maximum number of Ans :Manganese (Z = 25), as its atom has the maximum number of unpaired
oxidation states among the first series of transition metals electrons. i.e five ( +2 , +3 , +4 , +5 , +6 , +7)
OR , Which of the 3-d series of the transition metals exhibits
the largest number oxidation states and why?
Q.46 # Calculate the magnetic moment Ans-- With atomic number 25, the divalent ion in aqueous solution will have d5 configuration (five
of a divalent ion in aqueous solution if unpaired electrons). The magnetic moment, μ is μ = √5(5+2) = 5.92BM
its atomic number is 25.
Q.47 # Calculate the ‘spin only’ magnetic Ans—three unpaired electron .μ = √3(3+2) = 3.87 BM
moment of M2+ (aq) ion (Z = 27).
Q.48 # Name a member of the lanthanoid series which is well Ans—(a) Cerium (Z = 58) Ce4+ : Xe] 4f0 accounts for its formation .
known to (a) exhibit +4 oxidation state. (AI14) (b) Eu . Eu2+ is formed by losing the two s- electrons and its Xe] 4f7
(b) exhibit +2 oxidation state. (D-14) accounts for its formation .
Q.49 # Among the species Sc3+,.Ce4+, and Eu2+ Ans--In all the above ion the most stable oxidising state is +3 .therefore Sc3+ will remain
which one is good oxidising agent ? unchanged. Ce4+has the tendency to accept one electron to get the +3 oxidation state.
Sc3+ ——>[A r] 3d0 4s0 Hence Ce4+ is a good oxidising agent.Eu2+ has the tendency to lose one electron to get the
+3 oxidation state. Hence Eu2+ is a good reducing agent.
Ce4+ ——> [Xe] 4f0 5d0 6s0
Eu2+ ——>[Xe] 4f75d0 6s0
Q.50 # Mn (III) undergoes disproportionation Ans : Mn (III) unstable oxidation states , it undergoes disproportionation to Mn2+ and
reaction easily. MnO2 ( +4 oxidation states )
51 # Out of Mn3+ and Cr3+ , which is more Ans :- Mn3+ (3d4 4s0 , four unpaired d- electrons ) -- more paramagnetic - higher no. of
paramagnetic and why ? unpaired d- electrons Cr3+( 3d3 4s0 , three unpaired electron)
52# Which transition metal of 3d series has Ans :- Cu . The sum of high enthalpy of atomization and ionization enthalpy to transform
positive E0(M2+/M) value and why Cu(s) Cu2+(aq) is not balanced by hydration enthalpy .
53 # Sc is colourless in aqueous solution Ans :-Sc3+ have no unpaired d- electron . No d—d transition of unpaired d-electron . BUT Ti3+ have
3+

whereas Ti3+ is coloured (2014-F) one unpaired d- electron .d—d transition of unpaired d-electron in visible region . The
complementary colour is seen .
54# La3+ (Z = 57) and Lu3+ (Z = 71) do not show Ans: La3+ : (Xe] 4f0 and Lu3+ (Xe] 4f14 - absence of unpaired f- electrons for f—f transition .
any colour in solutions. so no f—f transition in the visible region .
55# Compare actinoids and lanthanoids with special (i) In Lanthanoids electrons are filled in antepenultimate shell i.e 4f subshell BUT in
reference to their : Actinoids 5f subshell
(ii) +3 , +2 and +4 ( do not show greater range of O .S ) BUT in Actinoids +3 , +4 , +5, +6 &7
(i) electronic configurations of atoms
(iiI) Lanthanoids are less reactive whereas Actinoids( low I.E) are more reactive chemically
(ii) oxidation states of elements (iv) Lanthanoids are smaller than the actinoids .
(iii) general chemical reactivity of elements.
(iv) atomic and ionic sizes
Q.56 # Calculate the number of unpaired electrons Mn2+ = 5 , Cr3+ = 3 , V3+ = 2 , Fe2+ = 4
in the following gaseous state ions: Mn2+, Cr3+, V3+ Cr3+ , due to half-filled configuration
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 are coloured in Cations are coloured in aqueous solutions:- V3+ (d1- )1-unpaired electron, Mn2+(d5) - 5
aqueous solutions and why? unpaired electron ,Ti3+(d1) - 1 unpaired electron, Fe3+(d5- 5 unpaired electron) and
Sc3+, V3+, Ti4+, Mn2+ ,Ti3+, Cu+, Fe3+ and Co2+. Co2+(d7) - 3 unpaired electron. Due to d-d transition of unpaired d- electrons
Q.58# Which metal in the first transition series (3d series) exhibits +1 Cu as Cu+
oxidation state most frequently and why?
Q.59# Generally there is an increase in Atomic size decreases from Ti to Cu .
density of elements from titanium (Z = 22) REASON:-Along a period ( 3d – series) Relative increase in nuclear charge is more dominant than
to copper (Z = 29) in the first series of relative increase in screening effect in d- subshell( imperfect screening)
transition elements. 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 the (Mn shows O.S from +2 to +7)—present in the middle of the series .
middle of a series of transition elements.
Q.61# There is a greater horizontal similarity in the properties of Atomic sizes are very close by along the d- series
the transition elements than of the main group elements.
Q.62# The third ionization enthalpy of Due to half –filled configuration.( extra stable- ) Removing third electron from Mn2+ needs
manganese (Z = 25) is exceptionally high. high I.E ( tightly held)
Q.63# Discuss the relative stability in Mn-- 3d5 4s 2 Due to half –filled configuration.( extra stable- )-- Mn2+ - -- 3d54s0
aqueous solutions of +2 oxidation state Cr--3d 4s5 1 ; Cr2+--3d 4 4s 0 (unstable)
3+
among the elements : Cr,Mn, Fe and Co. How Cr , Stable-due to half-filled configuration – Stable O.S. In aq. Solution
would you justify this situation? (At. Nos. Cr ( t2g3 eg0 ----- Higher crystal field stabilization energy ) CFT
= 24, Mn = 25, Fe = 26, Co = 27) Co--3d 7 4s 2 ; Co2+--3d 7 4s 0 (unstable)
Fe --3d 6 4s 2 ; Fe++- 3d 6 4s0 (unstable)
Q.64 # What may be the possible oxidation states of the 3d 3 4s 2--- (+2 ,+3 ,+5- stable)
transition metals with the following d electronic configurations 3d5 4s 2---( +2 , +3 , +4 , +5 , +6 , +7)
in the ground state of their atoms:
3d 3 4s 2 , 3d5 4s 2 and 3d 6 4s 2 . Indicate relative stability of 3d 6 4s 2 –(+2, +3)
oxidation states in each case.
Q.65 # Among the divalent cations in the first series of transition Ans : Due to highest number of unpaired d- electron ( i.e 5 ) [ 3d5 4s0 ]
elements, manganese 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 4f15d06s2 ; 57La3+—[Xe]54 4f05d06s0 -- fulfilled configurtaion
(i) The +3 oxidation state of 57La , 64Gd , 64Gd--- —[Xe]54 4f75d16s2 ; 64Gd3+--- —[Xe]54 4f75d06s0 -half –filled
14 1 2 3+ 4f145d06s0- fulfilled configuration
71Lu are especially stable . 71Lu----—[Xe]54 4f 5d 6s ; 71Lu ----—[Xe]54
(ii) Ce3+ can be easily oxidized to Ce4+ 4+
(ii)Due to fulfilled configuration of Ce - (Noble gas configuration- Configuration of Xe) –stable .
Ce3+ can be easily oxidized to Ce4+
Q.68# What are the characteristics of the 1. High enthalpy of atomization. 2. Show paramagnetism 3. Show colour compounds 4.
transition elements and why are they called Complex formation ability 5 . Show variable oxidation states .etc …( unique properties
transition elements? of Transitional metals)
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 due to half –filled and fulfilled
states exhibited by the lanthanoids? configuration of various ions.
Q. 70 # Which of the d-block elements may not be Zn , Cd and Hg - Due to absence of Unpaired d- electrons either in the ground
regarded as the transition elements? state or in their commonly found Oxidation states .
Q.71 # Name the oxometal anions of the first series of the transition metals in Permanganate ( MnO4 ¯ ) , +7-- Oxidation state , Mn
which the metal exhibits the oxidation state equal to its group number. belongs to 7th group .
Q.72 # How is the variability in oxidation states of Oxidation states in Transition metals differs by one
transition metals different from that of the non BUT , in Non- transition metals O.S differs by 2
transition metals? Illustrate with examples. Phosphorous - +3 and +5 ( as in P2O3 and P2O5 )
Iron – Fe2+ and Fe3+
Q.73 # What are interstitial Ans-- It because transition metals have voids in their crystal lattice , in which small atoms of H , C , N can fit
compounds? Why are such forming interstitial compounds which do not have fixed composition . The trapped atoms get bonded to the
compounds well known for atoms of TE .e.g. TiC , Fe3H , Mn4N ,VH0.56 TiH1.7 .
transition metals? ** 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 oxidation states in Mn-- 3d5 4s 2Mn2+ - -- 3d54s0(half –filled )
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 number of Hydrated ions (octahedral)–water is the ligand ( weak field – high spin complex ) Δ0< P
3d electrons in each of the following ions: Ti2+, Ti2+ ----(2 unpaired d- elctrons)3d24s0--- t2g2eg0
V2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+ and Cu2+. V2+--(3 unpaired d- elctrons)--3d34s0---- t2g3eg0
Indicate how would you expect the five 3d Cr3+--(3 unpaired d- elctrons)-3d34s0------ t2g3eg0
orbitals to be occupied for these hydrated ions Mn2+-(5 unpaired d- elctrons)3d54s0-- t2g3eg2
(octahedral). Fe2+--(4 unpaired d- elctrons)-3d64s0- t2g4eg2
Fe3+--(5 unpaired d- elctrons)-3d54s0-- t2g3eg2
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 Magnetic moment depends on spin and orbital motion of negatively charged unpaired electron .by
moment values of the following complex species ? knowing magnetic value we can predict the number of unpaired d- electron(s).
Spin –only formula , µ = [n(n+2)]1/2 = [1(1+2)]1/2 = 1.73 BM (example)
Example Magnetic Moment(BM) No.of unpaired electron configuration
Example Magnetic Moment (BM) K4[Mn(CN)6] 2.2 1 t2g5eg0 (Strong field) Oh--CFT
K4[Mn(CN)6] 2.2 [Fe(H2O)6] 2+ 5.3 4 t2g4eg2 (weak field)
[Fe(H2O)6]2+ 5.3 K2[MnCl4] 5.9 5 eg2t2g3(weak field)
K2[MnCl4] 5.9
Q.77 # Write the electronic configurations of the Atomic numbers 61--[Xe]544f 5 5d0 6s 2
elements with the atomic numbers 61, 91, 101, and 109. Atomic numbers 91--[Rn]86 5f 26d17s 2
Atomic numbers 101-[Rn]86 5f 136d07s 2
Atomic numbers 109 ---[Rn]86 5f 146d77s 2
Q.78# What are inner transition elements? Decide Lanthanoids ( 4f – series from 6th period and 3rd group) and actinoids( 5f – series from
which of the following At.nos are of the inner transition 7th period and 3rd group) are known as Inner transition elements :
elements :29, 59, 74, 95, 102, 104. Lanthanoids-- 59 Actinoids-- 95, 102
Q.79 # Sm2+ , Eu2+ and Yb+2 ions ** Sm+2(f 7) ,Eu+2(f 7),Yb+2(f 14)→ Sm+3,Eu+3, Yb+3 ( Stable , common O.S)
in solutions are good reducing (Sm2+ , Eu2+ and Yb+2 ions tendency to change into +3 O.S.)-- [ Acts as reducing agent)
agents but an aq. Solution of Ce4+ is ** Tb+4(f 7) , Ce+4(f0)→ Tb+3 , Ce+3 ( Stable , common oxidation states)
a good oxidizing agent (tendency to change into +3 O.S.)-- [ Acts as oxidizing agent]
Q.80 # The outer electronic configurations of two members of the Xe is the noble gas core whose atomic number is 54
lanthnoid series are as follows : 4f 1 5d 1 6s 2 and 4f 7 5d 0 6s 2 . [Xe]544f 1 5d 1 6s 2-- Atomic number is 58 ; stable O.S . +4 (empty conf.)
What are their atomic numbers?Predict the Oxidation States [Xe]544f 7 5d 0 6s 2-- Atomic number is 63 ; stable O.S +2 (half-filled conf.)
exhibited by these elements in their compounds . (AI-05)
Q.81 # Use Hund’s rule to derive the electronic configuration of 1
58Ce—[Xe]54 4f 5d 6s
0 0 Only one unpaired electron is present
Ce3+ ion, and calculate its magnetic moment on the basis of ‘spin- Spin –only formula , µ = [n(n+2)]1/2 = [1(1+2)]1/2 = 1.73 BM
only’ formula.
 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.) + 2 NaCl → MnO42– (manganate ion)
**The chromates and dichromates are interconvertible in STEP-2 :MnO42– (manganate ion) on Electrolytic oxidation in
aqueous solution depending upon pH of the solution. The alkaline solution → MnO4– ( permanganate ion)
oxidation state of chromium in chromate and dichromate is the same. KMnO4 is used as (1) a strong oxidant use in labs and industry
2 CrO42– + 2H+ → Cr2O72– + H2O as volumetric reagent in alkaline and acidic media
Cr2O72– + 2 OH- → 2 CrO42- (2) Disinfectant for well water
USES: K2Cr2O7 is used as (1) primary standard in volumetric (3) as bleaching agent for wood ,cotton ,silk and other textiles.
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 (Ferrous) → Fe+3 (Ferric) ,
+2 C 2O42 ˉ(oxalate) → CO2 (Carbon Dioxide)
Sn (stannous) →Stannic(Sn )
+2 +4

2# In neutral or faintly alkaline solution : Reduction half cell : MnO4ˉ + 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 no Year Sl Year
Complete and write the balanced no Complete and write the balanced
chemical equation chemical equation
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→