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Question -1

(a) (i) Which transition element in 3d series has positive E0M2+/M and why?
(ii) Name a member of lanthanoid series which is well know to exhibit +4 oxidation state and why?
(b) Account for the following :
(i) The highest oxidation state is exhibited in oxoanions of transition metals.
(ii) HCl is not used to acidify KMnO4 solution.
(iii) Transition metals have high enthalpy of atomisation. (Comptt. Delhi 2017)
Answer:
(a) (i) Copper has positive E0M /M value because the sum of enthalpies of sublimation and
2+

ionization is not balanced by hydration enthalpy.

(ii) Cerium shows +4 oxidation state because it acquires stable empty orbital configuration and
therefore Ce+4 is also used as a good analytical reagent and good oxidising agent.

(b) (i) The highest oxidation state shown in oxoanions of transition metals is Cr2O2−7 (Cr shows
+6) and it is due to the ability of oxygen to form multiple bonds with the metal atoms.
(ii) HCl is not used to the acidify KMnO4 solution because KMnO4 is a very strong oxidizing agent
and it can oxidize HCl to liberate chlorine gas.
(iii) In transition elements, there are large number of unpaired electrons in their atoms, thus they
have a stronger inter atomic interaction and thereby stronger bonding between the atoms. Due to
this they have high enthalpies of atomization.

Question -2
(a) Following are the transition metal ions of 3d series:
Ti4+, V2+, Mn3+, Cr3+
(Atomic numbers: Ti = 22, V= 23, Mn = 25, Cr = 24)
Answer the following:
(i) Which ion is most stable in an aqueous solution and why?
(ii) Which ion is a strong oxidising agent and why?
(iii) Which ion is colourless and why?
(b) Complete the following equations: (All India 2017)

Answer:
(a) (i) Cr3+ is most stable because of its small size and t32g configuration.
(ii) Mn3+ is a strong oxidising agent because after gaining one electron it is converted into
Mn2+ which has stable d5 configuration.
(iii) Ti4+ is colourless due to d° configuration, i.e., no unpaired electrons.

(b) (i) 2MnO4– + 16H+ + 5S2- → 2Mn2+ + 8H2O + 5S

Question -3.
(a) Account for the following:

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(i) Transition metals show variable oxidation states.
(ii) Zn, Cd and Hg are soft metals.
(iii) E° value for the Mn3+/Mn2+ couple is highly positive (+1.57 V) as compared to Cr3+/Cr2+.
(b) Write one similarity and one difference between the chemistry of lanthanoid and actinoid
elements. (All India 2017)
Answer:
(a) (i) The variability of oxidation state of transition elements is due to incompletely filled d-orbitals.
In transitional elements ns, and (n – 1) d electrons have a approximate equal energies hence in
addition to ns electrons, (n – 1) d electrons are also taking part in chemical bonding.

(ii) Zn, Cd and Hg are soft metals because they do not exhibit covalency due to completely filled d-
orbitals. Absence of unpaired d electrons causes weak metallic bonding.

(iii) Mn2+ exists in half-filled d5 state which is very stable while Mn3+ is d4 which is not so stable.
Mn3+ can be easily reduced to Mn2+. Conversion from d4 to d5 will be quick and have negative ΔG
value. Hence, because of the stability factor the E° value is high for this process. While Cr 3+ is d3 is
half-filled (t2g3) is stable in nature and Cr2+ is d4, has one extra electron which it would like to donate
to attain the stable half-filled (t2g3) configuration. Hence for the process Cr3+ to Cr2+, the value of E°
is less.

(b) Similarity: Both lanthanoids and actinoids show contraction in size and irregularity in their
electronic configuration.
Difference: Actinoids show wide rage of oxidation states but lanthanoids do not.

Question -4
The elements of 3d transition series are given as:
Se Ti V Cr Mn Fe Co Ni Cu Zn
Answer the following:
(i) Write the element which shows maximum number of oxidation states. Give reason.
(ii) Which element has the highest m.p.?
(iii) Which element shows only +3 oxidation state?
(iv) Which element is a strong oxidizing agent in +3 oxidation state and why? (All India)
Answer:
(i) Mn shows, maximum number of oxidation states upto +7. It has the maximum number of unpaired
electrons.
(ii) Cr has the highest melting point.
(iii) Sc shows only +3 oxidation state.
(iv) Mn is a strong oxidizing agent in +3 oxidation state because after reduction it attains +2 oxidation state
in which it has the most stable half-filled (d5) configuration.

Question -5

(a) How do you prepare :

(i) K2MnO4 from MnO2?
(ii) Na2Cr2O7 from Na2CrO4?
(b) Account for the following :
(i) Mn2+ is more stable than Fe2+ towards oxidation to +3 state.
(ii) The enthalpy of atomization is lowest for Zn in 3d series of the transition elements.
(iii) Actinoid elements show wide range of oxidation states. (Delhi 2014)

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Answer:
(a) (i) K2MnO4 from MnO2 (Pyrolusite) :
Finely powdered pyrolusite is fused with KOH in the presence of air to give green coloured
potassium manganate.

(b) (i) The 3d orbital in Mn2+ is half-filled and is more stable compared to Fe2+ has 6 electrons in the
3d orbital. Mn2+ prefer to lose an electron or get oxidised whereas Fe2+ will readily loose one
electron or get oxidised. Therefore, Mn2+ is much more resistant than Fe2+ towards oxidation.
(ii) As there are no unpaired electrons in zinc, it is soft and has low melting point and low enthalpy
of atomization.
(iii) Because of very small energy gap between 5f, 6d and 7s subshells all their electrons can take
part in bonding and shows variable oxidation states.

Question -6
(a) Describe the preparation of potassium permanganate from pyrolusite ore. Write balanced
chemical equation for one reaction to show the oxidizing nature of potassium permanganate.
(b) What is lanthanoid contraction and what is it due to? Write two consequences of lanthanoid
contraction. (Comptt. All India 2013)
Answer:
(a) Preparation of KMnO4 from pyrolusite ore occurs in two steps :
(i) Conversion of Mn02 into potassium manganate :

(ii) Oxidation of potassium manganate to potassium permanganate : The obtained potassium

manganate bubbled with carbon dioxide or chlorine or ozonised oxygen.

(b) Lanthanoid contraction : The overall decrease in atomic and ionic radii with increasing atomic
number is known as lanthanoid contraction. In going from La+3 to Lu+3 in lanthanoid series, the size
of ion decreases. This decrease in size in the lanthanoid series is known as lanthanoid
contraction. The lanthanoid contraction arises due to imperfect shielding of one 4f electron by
another present in the same subshell.

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Consequences :
(i) Similarity in properties: Due to lanthanoid contraction, the size of elements which follow (Hf –
Hg) are almost similar to the size of the elements , of previous row (Zr – Cd) and hence these are
difficult to separate. Due to small change in atomic radii, the chemical properties of lanthanoids
are very similar due to which separation of lanthanoid becomes very difficult.
(ii) Basicity difference: Due to lanthanoid contraction, the size decreases from La +3 to Lu+3. Thus
covalent character increases. Hence basic character of hydroxides also decreases i.e. why
La(OH)3 is most basic while Lu(OH)3 is least basic.

Question -7.
Give reasons :
(i) Zirconium (Z = 40) and Hafnium (Z = 72) have almost similar atomic radii.
(ii) d-block elements exhibit more oxidation states than f-block elements.
(iii) The enthalpies of atomization of the transition metals are high.
(iv) The variation in oxidation states of transition metals is of different type from that of the non-transition
metals.
(v) Orange solution of potassium dichromate
turns yellow on adding sodium hydroxide to it. (Comptt. All India 2013)
Answer:
(i) Zirconium and Hafnium have almost similar atomic radii due to the effect of lanthanoid contraction.
(ii) d-block elements exhibit more oxidation states due to small energy gap between ns and (n – 1)d
subshell while f – block elements show less oxidation state due to large energy gap between ns and (n -2)f
subshell.
(iii) Enthalpy of atomization is the amount of heat required to break the metal lattice to get free atoms. As
transition metals contain a large number of impaired electrons, they have strong interatomic attractions
(metallic bonds). Hence they have high enthalpies of atomization.
(iv) In transition elements, the successive oxidation state differs by unity, e.g, Mn shows all the oxidation
states from +2 to +7. On the other hand non-transition metals exhibit variable oxidation states which differ
by two units, e.g. Pb(II), Pb(IV), Sn(II), Sn(IV) etc.
(v) The orange coloured potassium dichromate solution when treated with basic NaOH solution, is
converted to chromate which gets a faint colour like yellow.
The reaction is given as:
K2Cr2O7 + 2NaOH → K2CrO4 + Na2CrO4 + H2O.
This formation of chromate (CrO4–) ion converts the colour of solution to yellow.

Question-8.
(a) Give reasons for the following :
(i) Mn3+ is a good oxidising agent.
(ii) E°M /M values are not regular for first row transition metals (3d series).
2+

(iii) Although ‘F is more electronegative than ‘O’, the highest Mn fluoride is MnF4, whereas the highest oxide
is Mn2O7.
(b) Complete the following equations : (All India 2013)

Answer:
(a) (i) Mn3+ has electronic configuration 3d44s0.
On reduction it gains one electron to become 3d54s0 which is half filled stable configuration. Hence it is a
good oxidising agent.

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(ii) E°M /M values are not regular for first row transition metals due to abnormalities and irregularities in their
2+

ionization enthalpies (IE1 + IE1) and sublimation enthalpies.

(iii) Because oxygen stabilizes the highest oxidation state even more than fluorine and has ability to form
multiple bonds with metal atoms.

Question-9.
(a) Describe the preparation of potassium dichromate from chromite ore. What is the effect of
change of pH on dichromate ion?
(b) How is the variability in oxidation states of transition elements different from that of non-
transition elements? Illustrate with examples. (Comptt. All India 2012)
Answer:
(a) Potassium dichromate is prepared from chromate by reacting chromite ore with Na2CO3
4 FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2 .
The yellow solution of sodium chromate is filtered off and acidified with H 2SO4 to give orange
sodium dichromate
2Na2CrO4 + 2H+ → Na2Cr2O7 + H2O + 2Na
Sodium dichromate is then treated with KCl to give potassium dichromate as orange crystals.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
The chromates and dichromates are interconvertible in aqueous solution depending upon pH of
the solution.
2CrO4-2 + 2H+ → Cr2O7-2 + H2O
Cr2O7-2 + 2OH–→ 2CrO4-2 + H2O

(b) In transition elements, the successive oxidation state differs by unity, e.g, Mn shows all the
oxidation states from +2 to +7. On the other hand, non-transition metals exhibit variable oxidation
states which differ by two units, e.g. Pb(II), Pb(IV), Sn(II), Sn(IV) etc.

Question -10
(a) Complete the following chemical equations :

(b) Explain the following observations :

(i) La3+ (Z = 57) and Lu3+ (Z = 71) do not show any colour in solutions.
(ii) Among the divalent cations in the first series of transition elements, manganese exhibits the
maximum paramagnetism.
(iii) Cu+ ion is not known in aqueous solutions. (All India 2010)
Answer:

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It has maximum five unpaired electrons, so maximum paramagnetism

(iii) Cu2+(aq) is much more stable than Cu+(aq). This is because although second ionization
enthalpy of copper is large but Δhyd (hydration enthalpy) for Cu2+(aq) is much more negative than
that for Cu+(aq) and hence it more than compensates for the second ionization enthalpy of copper.
Therefore, many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation as follows :
2Cu+ → Cu2+ + Cu

Question -11.
(a) Complete the following chemical equations :
(i) Cr2O2−7 (aq) + H2S (g) + H+ (aq) →
(ii) Cu2+ (aq) + I–(aq) →
(b) How would you account for the following :
(i) The oxidising power of oxoanions are in the order VO+2<Cr2O2−7<MnO−4
(ii) The third ionization enthalpy of manganese (Z = 25) is exceptionally high.
(iii) Cr2+ is a stronger reducing agent than Fe2+. (All India 2010)
Answer:
(a) (i) latex]\mathrm{Cr}_{2} \mathrm{O}_{7}^{2-}[/latex] + 3H 2S + 8H+ → 2Cr3+ + 7H2O + 3S
(ii) 2Cu2+ (aq) + 4I– (aq) → Cu2I2 + I2
(b) (i) The ions in which the central metal atom is present in the highest oxidation state will have
the highest oxidising power. In VO+2 V is present in the +5 oxidation state, while in Cr2O72- ion, Cr
is present in the +6 oxidation state. Similarly in the MnO4– ion, Mn is present in the +7 oxidation
state. Thus as the oxidation state of the central metal atom increases in the order V < Cr <Mn,
therefore the oxidising power of the oxoanions increases in the order
VO2+ < Cr2O72- < MnO4–
(ii) Because third electron has to be removed from stable half filled 3d-orbitals (Z = 25 has 3d 5 4s2).
(iii) Cr2+ is a stronger reducing agent than Fe2+ because E°Cr /Cr is negative (-0.41 V)
3+ 2+

whereas E°Fe /Fe is positive (0.77 V). Thus Cr2+ is easily oxidised to Cr3+ but Fe2+ cannot be easily
3+ 2+

oxidized to Fe3+.

Question -12
(a) What is meant by the term lanthanoid contraction? What is it due to and what consequences
does it have on the chemistry of elements following lanthanoids in the periodic table?
(b) Explain the following observations :

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(i) Cu ion is unstable in aqueous solutions.
+

(ii) Although Co2+ ion appears to be stable, it is easily oxidised to Co3+ ion in the presence of a
strong ligand.
(in) The E°Mn /Mn value for manganese is much more than expected from the trend for other
2+

elements in the series. (Delhi 2009)

Answer:
(a) Lanthanoid contraction : The overall decrease in atomic and ionic radii with increasing atomic
number is known as lanthanoid contraction.
Cause: As we move along the lanthanoid series, the effective nuclear charge increases on
addition of electrons and the electrons added in f-subshell causes imperfect shielding which is
unable to counterbalance the effect of the increased nuclear charge. Hence the contraction in size
occurs.
Consequences :
(i) Due to small change in atomic radii, the chemical properties of lanthanoids are very similar due
to which separation of lanthanoids becomes very difficult.
(ii) There is similarity in size of elements belonging to same group of second and third transition
series.
Example: Zr and Hf are known as chemical twins due to their similar radii.

(b) (i) Cu2+(aq) is much more stable than Cu+(aq). This is because although second ionization
enthalpy of copper is large but Δhyd (hydration enthalpy) for Cu2+(aq) is much more negative than
that for Cu+(aq) and hence it more than compensates for the second ionization enthalpy of copper.
Therefore, many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation as follows :
2Cu+ → Cu2+ + Cu
(ii) Co2+ ion is easily oxidised to Co3+ ion in presence of a strong ligand because of its higher crystal
field energy which causes pairing of electrons to give inner orbital complexes (d2sp3). Co3+ can
accomodate more no. of electrons from the ligand and offer better stability to the resulting
complex. Hence Co2+ oxidises to Co3+.
(iii) The value of E° for Mn is more negative than expected from the general trend due to greater
stability of half filled d-subshell (d5) in Mn2+.

Question -13
Give reasons:
(i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest oxidation
state of +4.
(ii) Transition metals show variable oxidation states.
(iii) Actinoids show irregularities in their electronic configurations. (Delhi 2016)
Answer:
(i) Because oxygen stabilizes the highest oxidation state (+7 of Mn) even more than fluorine i.e., +4 since
oxygen has the ability to form multiple bonds with metal atoms.
(ii) The variability of oxidation state of transition elements is due to incompletely filled d-orbitals and
presence of unpaired electrons.
(iii) This happens because the energy difference between 5f, 6d and 7s subshells of the actinoids is very
small and hence electrons can be accomodated in any of them.

Question -14
What is meant by ‘’disproportionation’? Give one example of disproportionation reaction in aqueous
solutions. (Comptt. All India 2015)
Answer:

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Disproportionation: When in a reaction, the oxidation of an element in a compound increases in one of the
products and decreases in the other product, it is said to undergo disproportionation of oxidation state. In
other words, the reaction in which an element undergoes self-oxidation and self-reduction simultaneously.
Example : In acidic solution Mn (VI) in MnO2−4
changes to Mn (VII) in the product MnO−4 and to Mn (IV) in the product MnO2.

Question -15.
Assign reasons for the following :
(i) Cu(I) ion is not known to exist in aqueous solutions.
(ii) Transition metals are much harder than the alkali metals.
(iii) From element to element actinoid contraction is greater than the lanthanoid contraction. (Comptt. All
India 2014)
Answer:
(i) Cu2+(aq) is much more stable than Cu+(aq). This is because although second ionization enthalpy of
copper is large but Δhyd (hydration enthalpy) for Cu2+(aq) is much more negative than that for Cu+(aq) and
hence it more than compensates for the second ionization enthalpy of copper. Therefore, many copper (I)
compounds are unstable in aqueous solution and undergo disproportionation as follows :
2Cu+ → Cu2+ + Cu
(ii) In transitional elements, in addition to metallic bonding there is extra covalent bonding due to presence
of unpaired electrons in their ‘d’ orbitals, hence they are much harder.
(iii) The actinoid contraction is greater than lanthanoid contraction due to poorer shielding of 5f electrons as
they are extended in space beyond 6s and 6p orbitals whereas 4f orbitals are buried deep inside the atom.

Question 16
Give reasons for the following :
(i) Transition metals exhibit a wide range of oxidation states.
(ii) Cobalt(II) is very stable in aqueous solutions but gets easily oxidised in the presence of strong ligands.
(iii) Actinoids exhibit a greater range of oxidation states than lanthanoids. (Comptt. All India 2014)
Answer:
(i) The variability of oxidation state of transition elements is due to incompletely filled d-orbitals as ns, and
(n – 1) d electrons have very less energy difference.
(ii) Co2+ ion is easily oxidised to Co3+ ion in presence of a strong ligand because of its higher crystal field
energy which causes pairing of electrons to give inner orbital complexes (d2sp3).
(iii) Actinoids because of very small energy gap between 5f, 6d and 7s subshells all their electrons can take
part in bonding and shows variable oxidation states.

Question -17.
How would you account for the following?
(i) The atomic radii of the metals of the third (5d) series of transition elements are virtually the same as
those of the corresponding members of the second (4d) series.
(ii) The E° value for the Mn3+/Mn2+ couple is much more positive than that for Cr3+/Cr2+ couple or
Fe2+/Fe2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride. (Delhi 2010)
Answer:
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(i) Due to lanthanoid contraction in second series after lanthanum, the atomic radii of elements of second
and third series become almost same and hence show similarities in properties.
(ii) The electronic configuration of Mn2+ ion is more symmetrical as compared to that of Cr2+ ion. So
3rd ionisation potential of Mn2+ is much higher. As a result E° value of Mn3+/ Mn2+ couple is much more
positive than for Cr3+/Cr2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride due to its high electronegativity.

Question -18
When a coordination compound CrCl3.6H2O is mixed with AgNO3 solution, 3 moles of AgCl are precipitated
per mole of the compound. Write :
(i) Structural formula of the complex
(ii) IUPAC name of the complex
(iii) Magnetic and spin behaviour of the complex (Comptt. All India 2017)
Answer:

Inner orbital complex so it is low spin complex.

Since 3 unpaired electrons are present, it is paramagnetic in nature.

Question -19
For the complex ion [CoCl2(en)2]+ write hybridization type and spin behaviour. Draw one of the
geometrical isomers of the complex ion which is optically active. [Atomic No.: Co = 27] (Comptt. All
India 2017)
Answer:
In the complex [CoCl2(en)2]+, 27Co3+ = [Ar]3d64s04p0

It is low spin complex.

Since inner d-orbitals are involved so it is an inner orbital complex.

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In this complex only cis-isomer shows optical isomerism

Question -20
For the complex ion [Fe(en)2Cl2]+ write the hybridization type and magnetic behaviour. Draw one of the
geometrical isomer of the complex ion which is optically active. [Atomic No.: Fe = 26] (Comptt. All India
2017)
Answer:
In the complex of 26Fe3+ = 3d54s0 4p0

Question-21.
For the complex ion [CoF6]3- write the hybridization type, magnetic character and spin nature.
[Atomic number: Co = 27] (Comptt. Delhi 2017)
Answer:
[CoF6]3-
Co3+ = [Ar] 3d6 4s0 4p6 .

It is paramagnetic due to presence of 4 unpaired electrons and form high spin complex.

Question-22.
For the complex ion [Ni(CN)4]2- write the hybridization type, magnetic character and spin nature.
[Atomic No.: Ni = 28] (Comptt. Delhi 2017)
Answer:
[Ni(CN)4]2-
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Ni = [Ar] 3d 4s 4p
2+ 8 0 0

∴ Diamagnetic due to paired electrons. Complex is low spin.

Question -23
(a) What type of isomerism is shown by the complex [Co(NH3)5 (SCN)]2+?
(b) Why is [NiCl24]2- paramagnetic while [Ni(CN)4]2- is diamagnetic? (Atomic number of Ni = 28)
(c) Why are low spin tetrahedral complexes rarely observed? (All India 2017)
Answer:
(a) [Co(NH3)5 (SCN)]2+ shows linkage isomerism.
(b) Since in [NiCl4]2- Cl– is a weak field ligand, it forms outer orbital complex and has unpaired electrons
which imparts paramagnetic character to complex while in [Ni(CN)4]2-, CN– is a strong field ligand, forms
inner orbital complex and has paired electrons which imparts diamagnetic character to it.
(c) Low spin tetrahedral complexes are rarely observed because orbital splitting energies for tetrahedral
complexes are not sufficiently large for forcing pairing.

Question -24.
(a) For the complex [Fe(H2O)6]3+, write the hybridization, magnetic character and spin of the
complex. (At. number: Fe = 26)
(b) Draw one of the geometrical isomers of the complex [Pt(en)2Cl2]2+ which is optically inactive. (All
India 2016)
Answer:
(a) [Fe(H2O)6]3+: The element Fe is in +3 oxidation state. As H2O is a weak field ligand, so electron

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pairing is not possible in this case.

Question-25.
(a) For the complex [Fe(CN)6]3- write the hybridization type, magnetic character and spin nature of
the complex. (At. number: Fe = 26).
(b) Draw one of the geometrical isomers of the complex [Pt(en)2Cl2]2+ which is optically active.
(Delhi 2016)
Answer:
(a) [Fe(CN)6]3-
The element Fe is in +3 oxidation state. As CN– ion is a strong field ligand, the electron pairing is

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possible in this case.

Question -26
Indicate the types of isomerism exhibited by the following complexes :
(i) [CO(NH3)5(NO2)]2+
(ii) [Co(en)3]Cl3 (en = ethylene diamine)
(iii) [Pt(NH3)2Cl2] (Comptt. Delhi 2015)
Answer:
(i) Linkage isomerism is shown by [CO(NH3)5(NO2)]2+
[CO(NH3)5(NO2)]2+
Pentaamminenitro Cobalt (III)
[CO(NH3)2(O-NO)]2+
Pentaamminenitrito-N-Cobalt (III)

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(ii) [Co(en)3]Cl3 shows optical isomerism

Question-27.
Write down the IUPAC names of the following complexes and also give stereochemistry and
magnetic moment of the complexes :
(i) [Co(NH3)5Cl]Cl2
(ii) [CrCl3(py)3]
(iii) K4[Mn(CN)6]
(At. nos. Cr = 24, Mn = 25, Co = 27, py = pyridine) (Comptt. All India 2013)
Answer:
(i) [Co(NH3)5Cl]Cl2
IUPAC name : Pentaamminechlorido cobalt (III) chloride
C.N. of Co = 6 Shape = octahedral
o.s. of Co : x + 0 – 1 = +2 x = +3

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Question-28.
Draw the structures of optical isomers of each of the following complex ions:
[Cr(C2O4)3]3-, [PtCl2(en)2]2+, [Cr(NH3)2Cl2(en)]+ (Comptt. Delhi 2013)
Answer:
Optical isomers of [Cr(C2O4)3]3-:
Name : Trioxalatochromate (III) ion

Optical isomers of [PtCl3(en)2]2+

Question-29
Write the IUPAC name and draw the structure of each of the following complex entities:

(At. nos. Cr = 25, Co = 27, Pt = 78) (Comptt. All India 2013)

Answer:
(i) IUPAC name : Trioxalato chromate (III) ion
(ii) IUPAC name : Hexa carbonyl chromium (o)
(iii) IUPAC name : Trichlorido ethylene platinum (II)

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Question-30
What is meant by crystal field splitting energy? On the basis of crystal field theory, write the
electronic configuration of d4 in terms of t2g and eg in an octahedral field when
(i) Δ0 > P
(ii) Δ0 < P (All India 2013)
Answer:
Crystal field splitting energy : When ligands approach the central metal ion, the degenerate d-
orbitals split into two sets, one with lower energy (t2g) and the other with higher energy (eg). The
difference of energy between these two sets of orbitals is called crystal field splitting energy. (Δ0
for octahedral complexes).
The magnitude of Δ0 decides the actual configuration of d-orbitals by the help of mean pairing
energy.

 If P > Δ0 then pairing of electrons does not occur and electrons enter in the higher energy e
orbitals and thus form high spin complexes due to weak field ligands.
 If P < Δ0 then pairing of electrons occurs within the same set and form low spin complexes
due to strong field ligands.

Question -31
(a) How is a double salt different from a complex?
(b) Write IUPAC names of the following :
(i) K3[Fe(C2O4)3]
(ii) [Pt(NH3)6]Cl4.
(c) Draw the structure of cis isomer of [CO(NH3)4Cl2]+ (Comptt. Delhi 2013)
Answer:
(a) Double salt dissociates completely into its constituent ions in their aqueous solution.
Example : KCl.MgCl2.6H2O dissociates into K+, Cl–, Mg2+ and H2O
Complex does not dissociate into its constituent ions.
Example : K4[Fe(CN)6] → 4K+ + Fe(CN)6]4-

(b) (i) K3[Fe(C2O4)3] IUPAC name : Potassium trioxalatoferrate (III)

(ii) [Pt(NH3)6]Cl4 IUPAC name : Hexaammine Platinum (IV) chloride

(c) Structure of cis isomer of [CO(NH3)4Cl2]+

Question-32
(a) Using Valence bond theory explain the geometry and magnetic behaviour by [Cr(NH3)6]3+ . (At.
no. Cr = 24)
(b) Write the IUPAC name of ionization isomer of [Ni(NH3)3NO3]Cl. (Comptt. Delhi 2013)
Answer:
(a) Cr atom (Z = 24), Ground state = [Ar] 3d5 4s1

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Geometry : Octahedral
Magnetic property : Paramagnetic
(b) IUPAC name : Triammine nitro nickel (II) Chloride

Question-33
(a) Give names of two complexes which are used in medicines.
(b) Using valence bond theory of complexes, explain the geometry and magnetic nature of
[Ni(CN)4]2-. (At. no. of Ni = 28) (Comptt. Delhi 2011)
Answer:
(a) (i) Cis – platin[Pt(NH3)2Cl2] is used in the treatment of cancer.
(ii) EDTA is used in the treatment of lead poisoning.

(b) [Ni(CN)4]-2 The electronic configuration of Ni is 3d84s2.

dsp2 hybridisation. The complex has square planar geometry and is diamagnetic in nature due to
absence of unpaired electrons.

Question -34
Name the following coordination entities and describe their structures :
(i) [Fe(CN)6]4-
(ii) [Cr(NH3)4Cl2]+
(iii) [Ni(CN)4]2-
(Atomic numbers Fe = 26, Cr = 24, Ni = 28) (All India 2011)
Answer:
(i) [Fe(CN)6]4-

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Name : Hexacyanoferate (II) ion

Question -35
Name the following coordination entities and draw the structures of their stereoisomers :
(i) [Co(en)2Cl2]+ (en = ethan-1, 2-diamine)
(ii) [Cr(C2O4)3]3-
(iii) [Co(NH3)3 Cl3] (Atomic numbers Cr = 24, Co = 27) (All India 2011)
Answer:
(i) [Co(en)2Cl2]+
Name : Dichloridobis (en = ethan-1, 2-diamine) Cobalt (III)

The geometrical isomers of [CoCl2(en)2]+ (2 isomers)

(ii) [Cr(C2O4)3]3-
Name : Trioxalatochromate (III) ion

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(iii) [Co(NH3)3 Cl3]

Name : Triamminetrichlorido cobalt (III)
Structure : The geometrical isomers of [Co(NH3)3Cl3] (2 isomers) :

Question -36
State a reason for each of the following situations :
(i) Co2+ is easily oxidized to Co3+ in presence of a strong ligand.
(ii) CO is a stronger complexing reagent than NH3.
(iii) The molecular shape of [Ni(CO)4] is not the
same as that of [Ni(CN)4]2- (Delhi 2011)
Answer:
(i) Because in the presence of strong ligands, the crystal field splitting energy is more than the energy
required to oxidise Co2+.
(ii) This is due to the formation of π – bond by back donation of electrons from metal to carbon of CO or
due to synergic bonding.
(iii) CO is a stronger field ligand than CN. Ni is in zero oxidation state in Ni(CO)4 and has tetrahedral
geometry. But, Ni is in +2 oxidation state in [Ni(CN)4]2- and has dsp2 hybridization (different geometry than
tetrahedral sp3).

Question -37
Write the structures and names of all the stereoisomers of the following compounds :
(i) [Co(en)3]Cl3
(ii) [Pt(NH3)2Cl2]
(iii) [Fe(NH3)4Cl2]Cl (All India 2011)
Answer:
(i) [Co(en)3]Cl3
Name ; Tris (ethane -1,2-diamine cobalt (III) chloride)
Hybridization : d2sp2 (∵ Coordination number = 6)
Shape : Octahedral
Magnetic behaviour : Diamagnetic

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(ii) [Pt(NH3)2Cl2]

Hybridization : dsp2( ∵ Coordination number = 4)

Name : Diamminedichlorido platinum (II) ion

Shape : Square planar

Magnetic behaviour : Diamagnetic
(iii) [Fe(NH3)4Cl2]Cl
Name : Tetraamminedichlorido Iron (III) chloride
Hybridization : d2sp3 (∵ Coordination number = 6)
Shape : Octahedral
Magnetic behaviour diamagnetic :

Question -38

Compare the following complexes’ with respect to structural shapes of units, magnetic behaviour and
hybrid orbitals involved in units :
(i) [Ni(CN)4]2- (ii) [NiCl4]2- (iii) [CoF6]3-
[At. Nos. : Ni = 28; Co = 27] (All India 2009)
Answer:
(i) [Ni(CN)4]2-

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Shape : Octahedral outer orbital complex

Hybridisation : sp3d2
Magnetic behaviour : Paramagnetic (4 unpaired electrons)

Question 39
Giving a suitable example for each, explain the following :
(i) Crystal field splitting
(ii) Linkage isomerism
(iii) Ambidentate ligand (All India 2009)
Answer:
(i) Crystal field splitting: It is the splitting of the degenerate energy levels due to the presence of
ligands. When ligand approaches a transition metal ion, the degenerate d-orbitals split into two
sets, one with lower energy and the other with higher energy. This is known as crystal field
splitting and the difference between the lower energy set and higher energy set is known as
crystal field splitting energy (CFSE)

Example : 3d5 of Mn2+

(ii) Linkage isomerism: When more than one atom in an ambidentate ligand is linked with central
metal ion to form two types of complexes, then the formed isomers are called linkage isomers and
the phenomenon is called linkage isomerism.
[Cr(H2O)5(NCS)]2+ Pentaaquathiocyanate chromium (III) ion
[Cr(H2O)5(NCS)]2+
Pentaaquaisothiocyanate chromium (III) ion

(iii) Ambidentate ligand: The monodentate ligands with more than one coordinating atoms is
known as ambidentate ligand. Monodentate ligands have only one atom capable of binding to a
central metal atom or ion. For example, the nitrate ion NO2– can bind to the central metal atom/ion
at either the nitrogen atom or one of the oxygen atoms.
Example : — SCN thiocyanate, — NCS isothiocyanate

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